JP2014208750A - Polyethylene resin composition for container and molded body comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene resin composition for a container which is excellent in blow moldability, environmental stress-cracking resistance and impact resistance, can be molded in a thinner thickness and lighter weight, has a high crystallization speed and high-speed moldability, achieves high cycle molding, has a high melt tension, excellent drawdown resistance and good pinch-off characteristics, can form a blow molded article of a complicated shape and has high solubility of resin components and excellent appearance of a molded body, and to provide a molded body comprising the same.SOLUTION: There is provided a polyethylene resin composition for a container which comprises: 10 to 40 wt.% of an ethylene-based polymer (II) which is polymerized using a metallocene-based catalyst containing Ti, Zr or Hf and has specific HLMFR and density values, and a long-chain branched structure based on 60 to 90 wt.% of a specific polyethylene (I) and satisfies specific properties (i) to (v).

Description

  The present invention relates to a polyethylene resin composition for containers and a molded body comprising the same, more specifically, it is excellent in hollow moldability, environmental stress crack resistance, impact resistance, thinner and lighter, Fast crystallization speed, excellent high-speed moldability, high molding cycle, high melt tension, excellent draw-down resistance, good pinch-off characteristics, and complex-shaped hollow molding are possible. The present invention relates to a polyethylene resin composition for containers having high compatibility of resin components and particularly excellent appearance of a molded article, and a molded article comprising the same.

In polyethylene hollow molding, injection molding, inflation molding, and extrusion molding, materials having good moldability and physical properties are generally required. Especially for hollow bottles commonly used as cosmetic containers, detergents, shampoos and rinse containers, or food containers such as edible oils, a polyethylene resin excellent in moldability, physical properties and chemical properties. Is widely used.
Further, in recent years, there has been a demand for lighter and thinner hollow bottles in order to reduce costs. In these hollow bottle applications, particularly excellent properties such as environmental stress crack resistance and impact strength are required. Yes. As polyethylene that satisfies such requirements, those having a relatively high molecular weight and a wide molecular weight distribution are suitable.

Polyethylene polymerized using a chromium-based catalyst has a relatively wide molecular weight distribution and a molecular structure having a long-chain branched structure, which makes it easy to hollow-mold, specifically, a high melt tension and swell ratio. In addition, since the pinch-off part of the hollow bottle is easily thickened uniformly, it is generally widely used as a hollow molding material.
In addition, polyethylene that has been two-stage polymerized using a titanium-based catalyst can impart excellent environmental stress crack resistance by selectively copolymerizing a comonomer with a high molecular weight component, and low Since the molecular weight and molecular weight distribution can be adjusted by controlling the molecular weight component, it is generally widely used as a high environmental stress cracking grade suitable for hollow molding.
And the polyethylene polymer composition which mixed the polyethylene polymerized in two steps using the titanium-type catalyst and the polyethylene polymerized using the chromium-type catalyst, and made use of the mutual advantage is disclosed (for example, patent document) 1-7).
However, as the weight of containers and the diversification of designs continue to increase, it is necessary to increase the density of polyethylene if the rigidity of the container is to be secured while the container is thinned, that is, the amount of comonomer copolymerization is suppressed. Since there is a need and it is contrary to the maintenance of the environmental stress crack resistance, there is still a demand for a material that has an excellent balance between rigidity and environmental stress crack resistance and can cope with the thinning.

Therefore, a polyethylene resin composition composed of multiple components is disclosed which includes polyethylene using a metallocene catalyst and has improved rigidity and environmental stress crack resistance balance (see, for example, Patent Documents 8 to 13).
However, polyethylene using a metallocene-based catalyst has a relatively narrow molecular weight distribution and a molecular structure having a uniform comonomer distribution. Since it has characteristics such as a low melt tension and a swell ratio, it is limited to use as a specific internal solution or a container having a specific shape.
Furthermore, as described in Patent Document 8, polyethylene using a metallocene-based catalyst has a low melting point and crystallization temperature corresponding to the same density, that is, it is easy to melt due to rigidity and is difficult to crystallize. The phenomenon that the speed is reduced is recognized, and there is a need to further increase the crystallization speed for high-speed molding.

Polyethylene containing a metallocene-based catalyst and polyethylene polymerized using a chromium-based catalyst are mixed, taking advantage of each other and having a good balance between rigidity and environmental stress crack resistance and suitable for hollow moldability A polymer composition is disclosed (for example, Patent Documents 14 to 16).
However, Patent Document 14 discloses that a low gel is obtained by mixing a polyethylene using a high molecular weight metallocene catalyst and a polyethylene polymerized using a chromium catalyst, and having good mechanical strength and moldability and compatibility of each component. However, the composition has a very high viscosity and is not suitable for high-speed moldability, and its application is limited to a large hollow molded container.
In Patent Documents 15 and 16, a composition having both mechanical strength and formability is obtained by mixing a composition containing polyethylene using a high molecular weight metallocene catalyst and polyethylene polymerized using a chromium catalyst. Although the composition has been disclosed, the compatibility of each component has not been sufficiently studied, and the molecular weight of polyethylene using a high molecular weight metallocene catalyst is too high or contributes to compatibility. Since the blended amount of polyethylene polymerized using a chromium-based catalyst is small, sufficient compatibility cannot be obtained, and the appearance of the molded product is not always sufficient.

On the other hand, for the purpose of further enhancing the environmental stress crack resistance of polyethylene using a metallocene catalyst, an increase in molecular weight is extremely effective, while compatibility with other polyethylene deteriorates, so polyethylene using a metallocene catalyst In the polyethylene resin composition containing, a resin design that achieves both compatibility and resistance to environmental stress cracking is important.
In view of such circumstances, while having the hollow moldability, high rigidity, impact resistance, etc. required for the conventional polyethylene resin composition for containers, the crystallization speed is fast, and high-speed molding high cycle can be achieved, Furthermore, there is a demand for a polyethylene material that is particularly excellent in the appearance of a molded product.

Therefore, the present applicant has found a polyethylene material having a high crystallization speed that can achieve further high speed molding and high cycle while having hollow moldability, high rigidity, impact resistance, etc. 2012-077681).
However, the hollow bottles generally used as described above have a surface property that is remarkably good depending on the use, and in many cases, those that are excellent in appearance are required. The appearance of the body was not fully examined, and the countermeasures were not sufficient.
Therefore, in this field, while having the hollow moldability, high rigidity, impact resistance, etc. required for the conventional polyethylene resin composition for containers, the crystallization speed is fast and further high-speed molding and high cycle can be achieved. In addition, there has been a demand for a polyethylene material that is remarkably excellent in appearance when formed into a molded body.

JP 59-196345 A JP 59-196346 A Japanese Unexamined Patent Publication No. 60-036547 JP 2004-059650 A JP 2004091739 A JP 2004-168817 A JP 2005-29881 A JP 08-283476 A Japanese Patent Laid-Open No. 08-283477 JP 2006-83370 A JP-A-11-106574 JP 11-199719 A JP 2009-7579 A JP 2003-213053 A Japanese Patent Laid-Open No. 11-138618 Special table 2009-506163

  In view of the above-mentioned problems of the prior art, the object of the present invention is excellent in hollow moldability, environmental stress crack resistance, impact resistance, thinner and lighter, and has a high crystallization speed. Excellent high-speed moldability, high cycle molding capability, high melt tension, excellent draw-down resistance, good pinch-off characteristics, complex-shaped hollow molding, and compatibility of resin components The object of the present invention is to provide a polyethylene resin composition for containers which is high and has a particularly excellent appearance of a molded article, and a molded article comprising the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have polymerized a polyethylene polymerized using a chromium catalyst, preferably polyethylene (I) having a specific property, with a metallocene catalyst. By blending a specific amount of ethylene polymer (II) with a specific property having a long chain branching structure and a specific melt flow rate ratio, it is excellent in hollow moldability, environmental stress crack resistance, and impact resistance. Thinner and lighter, can be molded at high speed, has a high crystallization speed, excellent high-speed moldability, can be molded into a high cycle, has high melt tension, excellent draw-down resistance, and good pinch-off characteristics. It has been found that a polyethylene resin composition for containers and a molded body comprising the same can be obtained, in addition to being capable of hollow molding in a complicated shape and having high compatibility of the resin components and particularly excellent appearance of the molded body. This has led to the completion of the present invention.

That is, according to the first invention of the present invention, 60 to 90% by weight of polyethylene (I) polymerized using a chromium catalyst is polymerized using a metallocene catalyst containing Ti, Zr or Hf. The melt flow rate (HLMFR) at a temperature of 190 ° C. and a load of 21.6 Kg is 0.2 g / 10 min or more and less than 5 g / 10 min, and the density (D) is 0.915 to 0.945 g / cm ³ , A polyethylene resin composition for containers, comprising 10 to 40% by weight of an ethylene-based polymer (II) having a long-chain branched structure and satisfying the following characteristics (i) to (v): Is provided.
Characteristic (i): Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 1 g / 10 min.
Characteristic (ii): HLMFR is 10 to 50 g / 10 min.
Characteristic (iii): Melt flow rate ratio (HLMFR / MFR) is 60-140.
Characteristic (iv): Density is 0.940-0.970 g / cm ³ .
Characteristic (v): Melt tension (MT, 190 ° C.) is 60 mN or more.

According to the second invention of the present invention, there is provided a polyethylene resin composition for a container according to the first invention, wherein the ethylene-based polymer (II) satisfies the following property (A): Is done.
Characteristic (A): Melt flow rate ratio (HLMFR / MFR) is 10-35.

According to a third aspect of the present invention, in the first or second aspect, the ethylene polymer (II) satisfies the following characteristics (b): a polyethylene resin composition for containers Is provided.
Characteristic (b): Dynamic melt viscosity (η _{H · 0.01} , unit: Pa · second) measured when the frequency ω is 0.01 rad / s at a temperature of 190 ° C. is 100,000 to 1,000,000. It is.

According to a fourth aspect of the present invention, in any one of the first to third aspects, the ethylene polymer (II) satisfies the following characteristics (c): polyethylene for containers A resin composition is provided.
Characteristics (c): Zero when a dynamic melt viscosity η ^* (unit: Pa · second) measured at a temperature ω of 190 ° C. in the range of 100 to 0.01 rad / s is approximated by the following formula (1) The shear viscosity (η ₀ , unit: Pa · second) is 100,000 to 1,000,000.
η ^* / η ₀ = 1 / {1+ (τ ₀ ω) ⁿ ) (1)
(In the formula (1), τ ₀ is a parameter representing the relaxation time, and n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region.)

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the polyethylene (I) satisfies the following characteristics (A) to (D): A polyethylene resin composition is provided.
Characteristic (A): MFR is 0.1 to 10 g / 10 min.
Characteristic (B): Melt flow rate (MLMFR) at a temperature of 190 ° C. and a load of 11.1 kg is 1 to 50 g / 10 min.
Characteristic (C): Melt flow rate ratio (MLMFR / MFR) is 10-30.
Characteristic (D): Density is 0.950 to 0.965 g / cm ³ .

According to a sixth aspect of the present invention, there is provided a polyethylene resin composition for a container characterized in that in any one of the first to fifth aspects, the following property (vi) is further satisfied. .
Characteristic (vi): Peak top time (T) and melting point (Tm) in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) satisfy the relationship of the following formula (2).
T [sec] ≦ −76.80 × Tm [° C.] + 10410 (2)

According to the seventh invention of the present invention, in any one of the first to sixth inventions, there is further provided a polyethylene resin composition for containers characterized by satisfying the following characteristic (vii): .
Characteristic (vii): Both an elongation viscosity η (t) (unit: Pa · second) and an elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed.

  According to the eighth invention of the present invention, in any one of the first to seventh inventions, the ethylene polymer (II) is a metallocene catalyst having a cyclopentadienyl ring and a heterocyclic aromatic group. There is provided a polyethylene resin composition for containers characterized by being polymerized.

  According to a ninth aspect of the present invention, there is provided the polyethylene resin composition for containers according to the eighth aspect, wherein the metallocene catalyst has an indenyl ring skeleton.

  Moreover, according to the 10th invention of this invention, the molded object characterized by using the polyethylene resin composition for containers of the invention in any one of the 1st-9th invention is provided.

  According to the eleventh aspect of the present invention, there is provided the molded body according to the tenth aspect, which is manufactured by a hollow molding method.

The polyethylene resin composition for containers according to the present invention is excellent in hollow moldability, environmental stress crack resistance and impact resistance, can be molded thinner and lighter, has a high crystallization speed, and is excellent in high-speed moldability. It can be molded in a high cycle, has high melt tension, excellent draw-down resistance, good pinch-off characteristics, can be used for complex-shaped hollow molding, and has high compatibility with resin components, There exists an effect that it is the polyethylene resin composition for containers excellent in an external appearance.
Furthermore, it is excellent in moldability, high fluidity, odor, food safety, rigidity, heat resistance and the like.
In addition, the molded body of the present invention is excellent in environmental stress crack resistance and impact resistance, thin and lightweight, excellent in odor, food safety, rigidity and heat resistance, and also has high compatibility of resin components, The surface properties of the molded body are excellent, and the appearance is good.
Therefore, it is suitable for applications such as containers that require such characteristics, and in particular, containers for cosmetic containers, detergents, shampoos and rinses, or food containers such as edible oils that are required to have a good appearance. It can use suitably for a use.
In particular, a container, which is a molded body using the polyethylene resin composition for containers of the present invention, can be molded at high speed and can be cycled, has excellent product characteristics, and is economically advantageous. Cosmetic containers and detergents It is suitable as a container for shampoos and rinses.

FIG. 1 is a plot diagram of typical elongation viscosity, and is a diagram for explaining a case where an inflection point of elongation viscosity is observed. FIG. 2 is a plot diagram of typical elongation viscosity, and is a diagram illustrating a case where an inflection point of elongation viscosity is not observed.

The polyethylene resin composition for containers of the present invention (hereinafter, also referred to as “polyethylene resin composition”) is a long chain polymerized with a metallocene catalyst and polymerized with polyethylene (I) using a chromium catalyst. It has a branched structure, has a specific melt flow rate ratio, contains a specific amount of ethylene polymer (II), and satisfies the requirements for specific physical properties. is there. Preferably, polyethylene (I) having a specific property is used.
Hereinafter, the present invention will be described in detail for each item.

1. Polyethylene (I)
In the present invention, polyethylene (I) needs to be polymerized using a chromium-based catalyst, and is preferably a homopolymer of ethylene and / or a copolymer of ethylene and α-olefin. More preferably, the polyethylene (I) satisfies the following characteristics (A) to (D).
Characteristic (A): Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 10 g / 10 min.
Characteristic (B): Melt flow rate (MLMFR) at a temperature of 190 ° C. and a load of 11.1 kg is 1 to 50 g / 10 min.
Characteristic (C): Melt flow rate ratio (MLMFR / MFR) is 10-30.
Characteristic (D): Density is 0.950 to 0.965 g / cm ³ .

When the MFR of polyethylene (I) is less than 0.1 g / 10 minutes, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. On the other hand, if the MFR exceeds 10 g / 10 min, impact resistance may not be ensured due to the effect of increasing the amount of low molecular weight components.
If the MLMFR of polyethylene (I) is less than 1 g / 10 minutes, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. On the other hand, if MLMFR exceeds 50, impact resistance may not be ensured due to the effect of increasing the amount of low molecular weight components.
Further, when the MLMFR / MFR of polyethylene (I) is less than 10, due to the narrow molecular weight distribution, the viscosity at a high shear rate is high, and the moldability may become a problem. On the other hand, when MLMFR / MFR exceeds 30, the impact resistance may be lowered due to the influence of the molecular weight distribution being too wide. The more preferable range of MLMFR / MFR of polyethylene (I) is 13 to 28, and the more preferable range is 15 to 25.
If the density of polyethylene (I) is less than 0.950, the rigidity of the container is inferior and the container tends to be deformed at a high temperature, and the container may be deformed and cause leakage due to the influence of the container internal pressure or the like. On the other hand, if the density exceeds 0.965, the environmental stress crack resistance of the container may be inferior.

The polyethylene (I) according to the present invention needs to be an ethylene polymer polymerized with a chromium catalyst, and an ethylene homopolymer is particularly preferable.
A chromium-based catalyst is used as the polymerization catalyst for the ethylene-based polymer. As an example of a preferable catalyst, at least a part of the catalyst is supported by supporting a chromium compound on an inorganic oxide carrier and activating it by firing in a non-reducing atmosphere. This is a chromium-based catalyst in which the chromium atom becomes hexavalent, and is generally known as a Philips catalyst. An overview of this catalyst can be found in M.C. P. McDaniel, Advances in Catalysis, Volume 33, 47, 1985, Academic Press Inc. , M.M. P. McDaniel, Handbook of Heterogeneous Catalysis, 2400, 1997, VCH, M.M. B. Welch et al., Handbook of Polyolefins: Synthesis and Properties, p. 21, 1993, described in documents such as Marcel Dekker.

The inorganic oxide carrier is preferably a metal oxide of Group 2, 4, 13 or 14 of the periodic table. Specific examples include magnesia, titania, zirconia, alumina, silica, tria, silica-titania, silica-zirconia, silica-alumina, or a mixture thereof. Of these, silica, silica-titania, silica-zirconia, and silica-alumina are preferable. In the case of silica-titania, silica-zirconia, silica-alumina, titanium, zirconium or aluminum atoms as metal components other than silica are 0.2 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to Those containing 5% by weight are used.
The preparation, physical properties and characteristics of the supports suitable for these chromium-based catalysts are described in C.I. E. Marsden, Preparation of Catalysts, Volume V, p. 215, 1991, Elsevier Science Publishers, C.I. E. Marsden, Plastics, Rubber and Composites Processing and Applications, Volume 21, p. 193, 1994, and the like.

The specific surface area of the support of the chromium-based catalyst before the activation of the firing is 250 to 1000 m ² / g, preferably 300 to 900 m ² / g, more preferably 400 to 800 m ² / g, so that the inorganic oxidation is performed. It is preferable to select a product carrier. When the specific surface area is less than 250 m ² / g, it is considered that the molecular weight distribution is narrow and long-chain branching is increased, but both durability and impact resistance may be lowered. In addition, a carrier having a specific surface area exceeding 1000 m ² / g may be difficult to produce.

The pore volume of the inorganic oxide support, as in the case of common chromium-based catalyst carrier used, 0.5~3.0cm ³ / g, preferably 1.0~2.0cm ³ / g More preferably, those in the range of 1.2 to 1.8 cm ³ / g are used. When the pore volume is less than 0.5, the pores become small due to the polymer during polymerization, and the monomer cannot be diffused, which may reduce the activity. A carrier having a pore volume exceeding 3.0 cm ³ / g may be difficult to produce.
The average particle size of the inorganic oxide carrier is 10 to 200 μm, preferably 20 to 150 μm, more preferably 30 to 100 μm, like the carrier used for general chromium catalysts.

  A chromium compound is supported on the inorganic oxide support. The chromium compound may be a compound in which at least a part of chromium atoms becomes hexavalent by firing activation in a non-reducing atmosphere after loading, such as chromium oxide, chromium halide, oxyhalide, chromate. , Dichromates, nitrates, carboxylates, sulfates, chromium-1,3-diketo compounds, chromic esters and the like. Specifically, chromium trioxide, chromium trichloride, chromyl chloride, potassium chromate, ammonium chromate, potassium dichromate, chromium nitrate, chromium sulfate, chromium acetate, tris (2-ethylhexanoate) chromium, chromium acetyl Examples include acetonate and bis (tert-butyl) chromate. Of these, chromium trioxide, chromium acetate, and chromium acetylacetonate are preferable. Even when a chromium compound having an organic group such as chromium acetate or chromium acetylacetonate is used, the organic group part burns by firing activation in a non-reducing atmosphere described later, and finally chromium trioxide is used. It is known that it reacts with the hydroxyl group on the surface of the inorganic oxide carrier in the same manner as in the case of at least some of the chromium atoms and becomes hexavalent and is fixed in the structure of chromate (VJ Ruddick). Et al., J. Phys. Chem., Volume 100, 11062, 1996, SM Augustine et al., J. Catal., Volume 161, 641, 1996).

  The chromium compound can be supported on the inorganic oxide support by a known method such as impregnation, solvent distillation, sublimation, etc., and an appropriate method may be used depending on the kind of the chromium compound to be used. The amount of the chromium compound to be supported is 0.2 to 2.0% by weight, preferably 0.3 to 1.7% by weight, more preferably 0.5 to 1.5% by weight with respect to the support as chromium atoms. is there.

  After the chromium compound is supported, it is fired and activated. The calcination activation can be performed in a non-reducing atmosphere substantially free of moisture, such as oxygen or air. At this time, an inert gas may coexist. Preferably, it is performed in a fluidized state using sufficiently dried air through which molecular sieves or the like are circulated. The firing activation is performed at 350 to 900 ° C., preferably 420 to 850 ° C., more preferably 450 to 800 ° C., for 30 minutes to 48 hours, preferably 1 hour to 36 hours, more preferably 2 hours to 24 hours. By this firing activation, at least a part of the chromium atoms of the chromium compound supported on the inorganic oxide support is oxidized to be hexavalent and chemically fixed on the support. If it is carried out below 350 ° C., the polymerization activity may be lost. On the other hand, if firing activation is performed at a temperature exceeding 900 ° C., sintering may occur and the activity may be reduced.

By using the chromium catalyst thus obtained, an ethylene polymer suitable for polyethylene (I) can be produced.
MLMFR and MFR are mainly adjusted by the polymerization temperature, the density is mainly adjusted by the amount of α-olefin, and can be applied to the ethylene polymer according to the present invention. That is, increasing the polymerization temperature can lower the molecular weight and consequently increase the HLMFR, and lowering the polymerization temperature can increase the molecular weight and consequently decrease the HLMFR.

The ethylene polymer is preferably an ethylene homopolymer, but ethylene and an α-olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- It can be obtained by copolymerization with pentene, 1-octene or the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like.
The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content therein is 0 to 1 mol%, preferably 0 to 0.1 mol%, more preferably 0 to 0.01 mol%.

  The ethylene-based polymer can employ any method such as slurry polymerization, liquid phase polymerization method such as solution polymerization, or gas phase polymerization method. In particular, the slurry polymerization method is preferable, and a pipe loop reactor is used. Either a slurry polymerization method used or a slurry polymerization method using an autoclave reactor can be used. Among these, a slurry polymerization method using a pipe loop reactor is preferable (details of a pipe loop reactor and slurry polymerization using the reactor are described in Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, page 148, 2001. (It is described in the Industrial Research Committee).

Liquid phase polymerization is usually carried out in a hydrocarbon solvent. As the hydrocarbon solvent, an inert hydrocarbon such as propane, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene or the like is used alone or as a mixture. In the gas phase polymerization method, a commonly known polymerization method such as a fluidized bed or a stirring bed can be employed in the presence of an inert gas, and a so-called condensing mode in which a medium for removing the heat of polymerization can coexist in some cases can also be employed. .
The polymerization temperature in the liquid phase polymerization method is generally 0 to 300 ° C., practically 20 to 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 150 ° C. The catalyst concentration and ethylene concentration in the reactor may be any concentration sufficient to allow the polymerization to proceed. For example, the catalyst concentration can range from about 0.0001 to about 5% by weight based on the weight of the reactor contents in the case of liquid phase polymerization. Similarly, the ethylene concentration can range from about 1% to about 10% based on the weight of the reactor contents for liquid phase polymerization.

  As a polymerization method, not only single-stage polymerization in which a single reactor is used to produce polyethylene, but also multistage polymerization can be performed by connecting at least two reactors in order to improve production. In the case of multi-stage polymerization, two-stage polymerization is preferred in which two reactors are connected and the reaction mixture obtained by polymerization in the first-stage reactor is continuously fed to the second-stage reactor.

  The ethylene used for polyethylene (I) may be ethylene produced from crude oil derived from ordinary fossil raw materials, or may be ethylene derived from plants. Examples of the plant-derived ethylene and polyethylene include ethylene and polymers thereof described in JP-T 2010-511634. Plant-derived ethylene and its polymers have the property of carbon neutral (does not use fossil raw materials and does not lead to an increase in carbon dioxide in the atmosphere), and can provide environmentally friendly products.

2. Ethylene polymer (II)
The polyethylene resin composition for containers according to the present invention comprises an ethylene polymer (II) polymerized using a metallocene catalyst containing Ti, Zr, or Hf with respect to 60 to 90% by weight of polyethylene (I). 10 to 40% by weight is contained.
The ethylene polymer (II) has a melt flow rate (HLMFR) of 0.2 g / 10 min or more and less than 5 g / 10 min at a temperature of 190 ° C. and a load of 21.6 kg, and a density of 0.915 to 0.945 g / cm. ³ and characterized by a molecular structure having a long-chain branched structure.

  The HLMFR of the ethylene-based polymer (II) needs to be 0.2 g / 10 min or more and less than 5 g / 10 min, preferably 0.3 to 1.0 g / 10 min, more preferably 0.00. The range is 4 to 0.7 g / 10 minutes. If this HLMFR is less than 0.2 g / 10 min, in the final resin composition, the HLMFR may not be within the specified range, and the fluidity may be reduced or the compatibility may be reduced. There is a risk of damaging the appearance. On the other hand, if the HLMFR is 5 g / 10 min or more, the final resin composition cannot achieve environmental stress crack resistance, and the long-term durability of the molded product may be reduced.

The density of the ethylene polymer (II) is required to be 0.915~0.945g / cm ^3, preferably 0.920~0.935g / cm ^3, more preferably 0.925 to 0 930 g / cm ³ . If the density is less than 0.915 g / cm ³ , the density range in the final resin composition cannot be achieved, the rigidity is insufficient, and the crystallization rate decreases, with the result that the molding cycle may decrease. . On the other hand, when the density exceeds 0.945 g / cm ³ , the environmental stress crack resistance may be lowered in the final resin composition.

The ethylene polymer (II) needs to have a long-chain branched structure. When the ethylene-based polymer (II) has a long-chain branched structure, it preferably corresponds to a case where an inflection point of elongational viscosity due to strain hardening is observed in the polyethylene resin composition for containers. That is, since the ethylene polymer (II) of the present invention has a long chain branched structure, the polyethylene resin composition for containers of the present invention is measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second). In the logarithmic plot of the extensional viscosity η (t) (unit: Pa · second) and the extension time t (unit: second), it is preferable that the inflection point of the extensional viscosity due to strain hardening is observed. By observing the inflection point, in the polyethylene resin composition for containers, there is an effect that the crystallization rate can be increased extremely effectively and the molding cycle is improved.
On the other hand, when the ethylene-based polymer (II) of the present invention does not have a long-chain branched structure, when combined with polyethylene (I), the crystallization rate of the polyethylene resin composition for containers is extremely effectively increased. There is a possibility that the effect of being able to be performed is not observed and the molding cycle is lowered.

In addition, since the ethylene-based polymer (II) of the present invention preferably has a molecular structure having a specific long-chain branched structure, an inflection point of elongation viscosity is preferably observed in the polyethylene resin composition for containers. And HLMFR / MFR is 10-35.
In general, when polyethylene has a long-chain branch structure, a component having a long relaxation time due to entanglement of long-chain branches increases. As a result, even in the same molecular weight and molecular weight distribution, the viscosity in the low shear region increases, so η ₀ (zero shear viscosity) shows a large value, MFR decreases, and HLMFR / MFR increases. That is, taking a large value of HLMFR / MFR is taken as one of the indicators suggesting an increase in long chain branching. Therefore, an inflection point of elongational viscosity is observed in the polyethylene resin composition for containers, and HLMFR / MFR is 10 to 35 in the ethylene polymer (II). ) Indicates a molecular structure having a specific long-chain branch structure controlled.

As described above, the ethylene-based polymer (II) of the present invention has a long-chain branched structure, and preferably satisfies the following property (A).
Characteristic (A): Melt flow rate ratio (HLMFR / MFR) is 10-35.
According to characteristic (a), HLMFR / MFR is preferably 30 or less, more preferably 25 or less, on the other hand, preferably 15 or more, more preferably 20 or more.
HLMFR / MFR has a strong correlation with the molecular weight distribution. When HLMFR / MFR takes a large value, the molecular weight distribution becomes wide, and when HLMFR / MFR takes a small value, the molecular weight distribution becomes narrow. When HLMFR / MFR exceeds 35, it is suggested that the influence of the long chain branched structure appears strongly, and the compatibility of each component may be deteriorated. That is, there is a possibility that the compatibility with polyethylene (I) is inferior, the surface properties of the molded article are not smooth, the appearance is inferior, and the physical properties such as impact resistance of the molded article are lowered. On the other hand, the lower limit is not particularly limited, but is preferably 10 or more for the reason that impact resistance and ESCR molecular weight distribution are required.

In the present specification, the presence or absence of an inflection point of elongational viscosity resulting from strain hardening can be observed in the measurement of the degree of strain hardening.
Regarding the method for measuring the strain hardening degree, as long as the uniaxial extensional viscosity can be measured, the same value can be obtained in principle by any method. For example, the measurement method and the measuring instrument are disclosed in publicly known document: Polymer 42 (2001) 8663. Details are described.
In the measurement of polyethylene according to the present invention, preferable measurement methods and measuring instruments include the following.

Measuring method:
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 0.1 / second-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and a thickness of 0.7 mm.

Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 0.1 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (Pa · second) on the vertical axis. On the log-log graph, the maximum elongation viscosity until strain becomes 4.0 after strain hardening is η _Max (t1) (t1 is the time when the maximum elongation viscosity is shown), and the extension viscosity before strain hardening. when the approximate line and η _linear (t), defines the value calculated as _{η Max (t1) / η linear} (t1) strain hardening degree and (.lambda.max). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time.
1 and 2 are typical plots of elongational viscosity. FIG. 1 shows a case where an inflection point of elongational viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows a case where an inflection point of elongational viscosity is not observed.

In addition, as described above, the ethylene polymer (II) of the present invention preferably satisfies the following characteristics (b).
Characteristic (b): Dynamic melt viscosity η ^* (η _{H · 0.01} , unit: Pa · second) measured at a temperature ω of 190 ° C. and a frequency ω of 0.01 rad / s is 100,000 to 1,000,000. It is.
According to the characteristic (b), the ethylene-based polymer (II) of the present invention preferably has a melt viscosity (η _{H · 0.01} , unit: Pa) with a frequency ω of 0.01 (unit: rad / s). -Sec) is preferably less than 1,000,000. More preferably, it is smaller than 800000, More preferably, it is smaller than 600000. On the other hand, the lower limit is not particularly limited, but is preferably 100,000 or more for the reason that an appropriate molecular weight is required in order to maintain high environmental stress crack resistance in the final resin composition. More preferably, it is 200000 or more, More preferably, it is 400000 or more. When the melt viscosity is 1,000,000 or more, since the viscosity ratio between the ethylene polymer (II) and the polyethylene (I) is too large, the effect of excellent compatibility with the polyethylene (I) is not observed. There exists a possibility that physical properties, such as an impact resistance, may be inferior to the external appearance of a molded article.

The ethylene polymer (II) of the present invention preferably has an HLMFR / MFR of 35 or less and is excellent in compatibility with polyethylene (I), but more preferably has a low strain rate. Since the viscosity of the ethylene polymer (II) can be kept low because the melt viscosity of the region frequency ω is 0.01 (unit: rad / s) or less, the viscosity of the ethylene polymer (II) can be kept low. Since the viscosity ratio between (I) and the high-viscosity ethylene polymer (II) can be kept small, it is considered that the compatibility is further improved.
The method for measuring the melt viscosity at a frequency ω of 0.01 (unit: rad / s) is the same as the method for measuring strain hardening described above, and preferable measuring methods and measuring instruments include those described above. And can be obtained with a rheometer (eg, Ales from Rheometrics).
In addition, the melt viscosity of the ethylene polymer (II) having a frequency ω of 0.01 (unit: rad / s) can be generally adjusted by molecular weight, molecular weight distribution, long chain branching, and the like. Therefore, in order to obtain a melt viscosity having a specific range, a long chain branched structure having a specific molecular weight and molecular weight distribution and appropriately controlled may be used. By using it, it can manufacture suitably.

As described above, the ethylene polymer (II) of the present invention preferably satisfies the following characteristics (c).
Characteristic (c): Zero shear viscosity when the dynamic melt viscosity η ^* (Pa · s) measured at a temperature ω of 190 ° C. in the range of 100 to 0.01 rad / s is approximated by the following equation (1) η (Pa · s) is 100,000 to 1,000,000.
η ^* / η ₀ = 1 / {1+ (τ ₀ ω) ⁿ ) (1)
(In the formula (1), τ ₀ is a parameter representing the relaxation time, and n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region.)
According to the characteristics (c), the ethylene polymer (II) of the present invention preferably has a zero shear viscosity (η ₀ , unit: Pa · second) smaller than 1000000. More preferably, it is smaller than 800000, More preferably, it is smaller than 600000. On the other hand, the lower limit is not particularly limited, but is preferably 100,000 or more for the reason that an appropriate molecular weight is required in order to maintain high environmental stress crack resistance in the final resin composition. More preferably, it is 200000 or more, More preferably, it is 400000 or more. When the zero shear viscosity is 1,000,000 or more, the viscosity ratio between the ethylene polymer (II) and the polyethylene (I) becomes too large, so that the effect of excellent compatibility with the polyethylene (I) is not observed. Further, the appearance of the molded product is inferior, and physical properties such as impact resistance may be deteriorated.

The zero shear viscosity η ₀ (unit: Pa · s) is defined as the shear viscosity at zero shear flow, and in this specification, together with the relaxation time τ ₀ (s), ANTEC '94 (The Society of Plastics Engineers, 1994). ), Page 1814 (by S. Lai et al.), A value obtained by approximating the dynamic melt viscosity η ^* (unit: Pa · s) with the cloth viscosity formula (the following formula (1)). Here, the dynamic melt viscosity η ^* is in the range of a plate interval of 1.0 mm using a parallel plate at 190 ° C., a strain of 0.2 to 1%, and a frequency ω of 100 to 0.01 (unit: rad / s). Which can be obtained with a rheometer (Ares manufactured by Rheometrics), and the approximation of the result to the following equation (1) is made by using a computer program commercially available by the regression method. Can be calculated.
η ^* / η ₀ = 1 / {1+ (τ ₀ ω) ⁿ } (1)
In the above formula (1), n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region, and τ0 is a parameter indicating the relaxation time.

In general, when melt-mixing polyethylenes having different molecular weights, in other words, polyethylenes having different viscosities, the smaller the viscosity ratio of the two, the easier to mix, and when the viscosity ratio becomes too large, It is known that the component is unevenly distributed due to poor dispersion and becomes a gel, which causes poor appearance. For example, more detailed research has been conducted on Newtonian fluids. When liquids with different viscosity ratios are mixed, the conditions for the dispersion of high-viscosity liquids: the number of capillaries depends on the kneading mode and the viscosity ratio of the two. It has been reported that it can be arranged (HP Grace: Chem. Eng. Commun., 14, 225 (1982)). It is also reported that when the same strain is applied to a system in which liquids with different viscosity ratios are mixed, the higher the viscosity ratio, the lower the strain rate of the high-viscosity liquid and the cause of poor dispersion. (A. Biswas et al .: SPE-ANTEC, 336 (1994)).
On the other hand, since polyethylene resins and the like are non-Newtonian fluids, the viscosity depends on the shear rate, so the above knowledge cannot be applied simply, but it is considered that the above knowledge can be referred to. Therefore, in the dispersion of polyethylene having a large viscosity ratio, it is considered that the viscosity in the region where the strain rate of the high viscosity component is small is an important factor, and the viscosity in the region where the strain rate of the resin is small is within the scope of the present invention. In this case, it is presumed that the ethylene polymer (II) is highly dispersed in the polyethylene (I).
Further, the value of the zero shear viscosity η0 of the ethylene polymer (II) can be generally adjusted by molecular weight, molecular weight distribution, long chain branching, and the like. Therefore, in order to obtain the zero shear viscosity η ₀ in a specific range, a long chain branched structure having a specific molecular weight and molecular weight distribution and appropriately controlled may be used. By using the catalyst, it can be suitably produced.

  From the above, it is considered that the resin composition containing a component having a long-chain branched structure may have poor compatibility. However, even if it has a long-chain branch structure, the length and / or number of long-chain branches can be obtained by using a specific melt flow rate ratio (HLMFR / MFR) and further a component having specific viscosity characteristics. In the resin composition, while the compatibility is improved, the effect of having a long-chain branched structure is also exhibited, and the effect of the present invention as described above is exhibited. It was found.

The ethylene polymer (II) having a long chain branched structure according to the present invention is not particularly limited as a production method, but preferably has a specific metallocene catalyst, that is, a metallocene complex having a specific structure as a polymerization catalyst. It can manufacture by polymerizing using a catalyst.
In addition, as the ethylene polymer (II) having a long-chain branched structure, polyethylene having a terminal vinyl group (macromonomer) is generated by chain transfer to ethylene, and a long-chain is obtained through copolymerization of the macromonomer and ethylene. A polymer having a branched structure can be obtained.
Among the metallocene catalysts, a catalyst having a metallocene complex having a specific structure is preferred, and in particular, a metallocene complex having a cyclopentadienyl ring and a heterocyclic aromatic group, or a metallocene complex having a cyclopentadienyl ring and a fluorenyl ring. preferable.

  The ethylene polymer (II) needs to be polymerized with a metallocene catalyst containing Ti, Zr or Hf. Examples of the metallocene catalyst include a combination of a co-catalyst and a complex called a metallocene complex in which a ligand having a cyclopentadiene skeleton is coordinated to a transition metal. Specific metallocene catalysts include metallocene complexes formed by coordination of a ligand having a cyclopentadiene skeleton such as methylcyclopentadiene, dimethylcyclopentadiene, and indene with transition metals including Ti, Zr, Hf, and the like. Examples of the catalyst include a combination of organic metal compounds of Group 1 to Group 3 elements such as aluminoxane, and a supported type in which these complex catalysts are supported on a carrier such as silica.

The metallocene catalyst used in the present invention includes the following components (A) and (B), and is a catalyst combined with the component (C) as necessary.
Component (A): Metallocene complex Component (B): Compound that reacts with component (A) to form a cationic metallocene compound Component (C): Fine particle carrier

(1) Component (A)
As the component (A), a metallocene compound of a Group 4 transition metal is used. Specifically, compounds represented by the following general formulas (I) to (VII) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY (I)
^{_{Q 1 (C 5 H 4-}} c R 1 c) (C 5 H 4-d R 2 d) MXY (II)
^{_{Q 2 (C 5 H 4-}} e R 3 e) ZMXY (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW (V)
^{_{Q 3 (C 5 H 5-}} g R 4 g) (C 5 H 5-h R 5 h) MXY (VI)
^{_{Q 4 Q 5 (C 5 H}} 3-i R 6 i) (C 5 H 3-j R 7 j) MXY (VII)

Here, Q ¹ , Q ⁴ and Q ⁵ are binding groups that bridge two conjugated five-membered ring ligands, Q ² is a binding group that bridges conjugated five-membered ring ligands and Z groups, Q ³ is a bonding group that bridges R ⁴ and R ⁵ , M is a transition metal of Group 3-12 of the periodic table, X, Y, and W are each independently hydrogen, halogen, C 1-20 Hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing carbon atom having 1 to 20 carbon atoms Z represents oxygen, a ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. Indicates. M is a Group 4 transition metal such as Ti, Zr, or Hf.

R ^{1 to} R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an oxygen-containing hydrocarbon group, silicon A hydrocarbon-containing group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; Among these, it is preferable that at least one of R ^{1 to} R ⁵ is a heterocyclic aromatic group. Among the heterocyclic aromatic groups, a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group are preferable, and a furyl group and a benzofuryl group are more preferable. These heterocyclic aromatic groups include hydrocarbon groups having 1 to 20 carbon atoms, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups, and phosphorus-containing carbon groups. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. Also, two adjacent R ¹ , 2 R ² , 2 R ³ , 2 R ⁴ , 2 R ⁵ , 2 R ⁶ , or 2 R ⁷ are bonded to each other. Thus, a ring having 4 to 10 carbon atoms may be formed. a, b, c, d, e, f, g, h, i, and j are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 0 ≦ e ≦, respectively. 4, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h ≦ 5, 0 ≦ i ≦ 3, 0 ≦ j ≦ 3.

A binding group Q ¹ , Q ⁴ , Q ⁵ that bridges between two conjugated five-membered ring ligands, a binding group Q ² that bridges a conjugated five-membered ring ligand and a Z group, and R Specific examples of Q ³ that crosslinks ⁴ and R ⁵ include the following. Methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenyl Silicon-containing crosslinking groups such as silylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, germanium-containing crosslinking group, alkylphosphine, amine, etc. . Among these, an alkylene group, an alkylidene group, a silicon-containing crosslinking group, and a germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are exemplified below. Alternatively, a compound substituted with Ti can be used in the same manner. In addition, the metallocene complexes represented by the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are compounds represented by the same general formula or different general formulas. It can be used as a mixture of two or more compounds represented by the formula.

Compounds of general formula (I) Biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5-benzoin Denyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azurenyl) zirconium dichloride, bis (2-methyl-4H-azurenyl) cyclopentadienylzirconium dichloride, bis (2-methylbiscyclopentadienylzirconium) Dichloride, bis (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride, bis (2-furylcyclo) Pentadienyl) zirconium dichloride, bis (2-furylindenyl) zirconium dichloride, bis (2-furyl-4,5-benzoindenyl) zirconium dichloride.

Compounds of general formula (II) Dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2-methylindenyl)] zirconium dichloride, dimethylsilylene bis [1, 1 '-(2-methyl-4-phenyl-indenyl)] zirconium dichloride, ethylene bis [1,1'-(2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylene bis [1,1 '-(2-Methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1,1'-(2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis {1,1'- [2-Methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dic Lido, dimethylsilylene bis [1,1 '- (2-ethyl-4-phenyl -4H- azulenyl)] zirconium dichloride, ethylene bis [1,1' - (2-methyl -4H- azulenyl)] zirconium dichloride.
Dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2-furyl) -4,5-dimethyl-cyclopentadienyl] ]} Zirconium dichloride, dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride, dimethylsilylenebis {1,1 '-[2- (2-furyl) indenyl]} zirconium dichloride, dimethylsilylenebis {1,1'-[2- (2-furyl) -4-phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1, 1 ′-[2- (2- (2- (5-methyl) furyl) -4-phenyl-indenyl]} zirconium dichloride, di Tylsilylenebis {1,1 ′-[2- (2- (5-methyl) furyl) -4- (4-isopropyl) phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2 -(5-methyl) furyl) -4- (4-t-butyl) phenyl-indenyl]} zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-Fluorenyl) zirconium dichloride, diphenyl Methylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) [9 -(2,7-t-butyl) fluorenyl] zirconium dichloride.

Compound of general formula (III) (t-Butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η5-cyclopentadienyl) -1 , 2-ethanediyl-zirconium dichloride, (ethylamide) (tetramethyl-η5-cyclopentadienyl) -methylenezirconium dichloride, (t-butylamido) dimethyl- (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, ( t-butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dichloride, (phenylphosphine) Id) dimethyl (tetramethyl-η5-cyclopentadienyl) silane zirconium dibenzyl.

Compound of general formula (IV) (cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (Cyclopentadienyl) (2,6-di-t-butylphenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride.

Compounds of general formula (V) (cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) Zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triisopropoxide.

Compound of general formula (VI) Ethylene bis (7,7'-indenyl) zirconium dichloride, dimethylsilylene bis {7,7 '-(1-methyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {7, 7 ′-[1-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, dimethylsilylenebis [7,7 ′-(1-ethyl-3-phenylindenyl)] zirconium dichloride, dimethylsilylenebis {7 , 7 '-[1-Isopropyl-3- (4-chlorophenyl) indenyl]} zirconium dichloride.

Illustrative examples of complexes comprising compound (i) secondary carbon of general formula (VII):
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CHMe 2) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η _{^{5 -C 5 H-3,5- (CHMe}} 2) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CHMe}} 2) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (M ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (CHMe 2) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H _{-3- (CHMe 2) -5-Me} } 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (CHMe 2) -5-Me} 2 Zr (n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 _{H-3- (CHMe 2) -5} -Me} 2 Zr (CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{2 ZrCl 2, (Me 2 Si} ) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{ZrMe 2, (Me 2 Si)} 2 {η 5 -C 5 H-3,5- (2- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 - C ₅ H-3,5- (2- _{adamantyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- adamantyl) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 { _{^{η 5 -C 5 H-3- (}} 2- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{2-adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2,

meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (2-adamantyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(2-adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H _{9) 2, meso- (Me 2} Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {Η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrMe ₂ , (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3,5- ( _{cyclohexyl) 2 2 Zr (n-C 4 H} 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{cyclohexyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5 _{-Me} 2 ZrMe 2, rac- (} Me 2 Si) 2 {η 5 -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(cyclohexyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 ^{_{i) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5-Me } ₂ Zr (n-C ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (cyclohexyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

(Ii) Examples of compounds containing tertiary carbon:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CMe 3) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η ^{_{5 -C 5 H-3,5- (CMe}} 3) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CMe}} 3) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (Me 2 Si) 2 ^{_{η 5 -C 5 H-3- (}} CMe 3) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe _{3) -5-Me} 2 ZrCl} 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (CMe ₃ ) -5-Me} ₂ Zr (nC ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{CMe 3) -5-Me} 2} Zr (CH 2 C 6 H 5) 2,
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1- _{adamantyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- (1- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2 , Meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1,1- _{dimethylpropyl) 2} 2 ZrCl 2, (} Me ^{_{Si) 2 {η 5 -C 5}} H-3,5- (1,1- _{dimethylpropyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- (1, _{1-dimethylpropyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (1,1- _{dimethylpropyl) 2}} 2 Zr ( _{CH 2 C 6 H 5) 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (1,1- _{dimethylpropyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1, _{1-dimethylpropyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H 3- _{(1,1-dimethylpropyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1,1- dimethylpropyl) -5-Me } ₂ ZrMe ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (n—C ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

(Iii) Examples of compounds containing an alkylsilyl group:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- ( _{dimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η _⁵ -C ⁵ H-3,5- _{(dimethylsilyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethylsilyl) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η _⁵ -C ⁵ H-3- _{(butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , meso- (Me ₂ Si) ₂ { η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} _{2 ZrMe 2, meso- (Me 2 Si} ) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- ( _{trimethylsilyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3 5- _{(trimethylsilyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{trimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (trimethylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 { η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ Zr ( _{n-C 4 H 9) 2} , rac- ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H 3- _{(trimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2}} 2 ZrCl 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5 (Diphenyl _{silyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (diphenylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (Diphenylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si ) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (n-C ₄ H ₉ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3 - (diphenyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) _{, Meso- (Me 2 Si) 2} {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- _{(butyldiphenylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (phenylmethyl _{silyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2}} 2 ZrMe 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5- ( Fe _{Rumechirushiriru) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2} 2 Zr (CH 2} C 6 H 5 ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (phenylmethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H 3- (phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} n- _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( Fenirumechi _{Silyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) ₂ {η ⁵ -C ₅ H-3- (phenylmethylsilyl) -5-Me} ₂ Zr (nC ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3 - (phenylmethyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, a.

Among these, a compound of a combination of secondary carbon and primary carbon is preferable, and rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (CHMe ₂ ) — is more preferable. _{5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {η 5 _{-C 5 H-3- (CHMe 2} ) -5-Me} 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2 Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(dimethylsilyl) -5-Me} 2 ZrMe 2} , meso _{(Me 2 Si) 2 {η} 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethyl silyl ) -5-Me} ₂ ZrMe ₂ .
In addition, the compound which replaced the silylene group of the compound of these specific examples with the germylene group is illustrated as a suitable compound.
As specific examples of the metallocene complex, JP-A-7-188335, Journal of American Chemical Society, 1996, Vol. A transition metal compound having a ligand containing one or more elements other than carbon in a 5-membered ring or a 6-membered ring disclosed in 118, 2291 can also be used.
An example of a metallocene complex having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3675509.

Among the transition metal compound components (A) described above, preferred metallocene complexes for producing the ethylene-based polymer (II) include metallocene complexes represented by general formula (I) or general formula (II) Among them, a metallocene complex having a cyclopentadienyl ring and a heterocyclic aromatic group is preferable, and a metallocene complex having an indenyl ring skeleton is more preferable. A metallocene complex represented by the general formula (II) is preferred from the viewpoint of being able to produce a high molecular weight polymer and having excellent copolymerizability in the copolymerization of ethylene and another α-olefin. A metallocene complex represented by the above and having an indenyl ring skeleton is most preferable. The ability to produce a high molecular weight product has the advantage that polymers with various molecular weights can be designed by adjusting the molecular weight of various polymers as described below.
Furthermore, the following compound groups are preferable among the metallocene complexes represented by the general formula (II) from the viewpoint that a polyethylene having a high molecular weight and a long chain branch can be produced.

As an example of a preferable embodiment, the compound group is a bridged metallocene complex containing at least one heterocyclic aromatic group in the compound as R ^{1 to} R ² . Preferred heterocyclic aromatic groups include the group consisting of a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group. These substituents may further have a substituent such as a silicon-containing group. Of the substituents selected from the group consisting of a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group, a furyl group and a benzofuryl group are more preferable. Further, these substituents are preferably introduced at the 2-position of the substituted cyclopentadienyl group or the substituted indenyl group, and at least one other substituted cyclopentadienyl group having no condensed ring structure is introduced. It is particularly preferred that the compound has.

  By using these compounds as a metallocene complex, and by employing specific polymerization conditions, the ethylene polymer (II) preferred in the present invention can be easily produced.

  These metallocene complexes are preferably used as supported catalysts as described later. In the first group of compounds, the furyl group interacts with the so-called heteroatom contained in the thienyl group and the solid acid on the support, causing non-uniformity in the active site structure and easily generating long chain branching. I think. Also in the second compound group, it is thought that the use of a supported catalyst changed the space around the active site, so that long chain branching was easily generated.

(2) Component (B)
The method for producing an ethylene-based polymer (II) according to the present invention includes a metallocene compound (component (A), hereinafter simply referred to as A) as an essential component of an olefin polymerization catalyst, in addition to the component (A). And a compound that forms a cationic metallocene compound (component (B), hereinafter may be simply referred to as B), and a fine particle carrier (component (C), hereinafter). , And may be simply written as C.).

As one of the compounds (B) that react with the metallocene compound (A) to form a cationic metallocene compound, an organoaluminum oxy compound can be mentioned.
The organoaluminum oxy compound has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any compound represented by the following general formula (5) can be used, but trialkylaluminum is preferably used.
R ⁵ _t AlX ³ _3-t (5)
(In the formula (5), R ⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ³ represents a hydrogen atom or a halogen atom. Represents an atom, and t represents an integer of 1 ≦ t ≦ 3.)

The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. It is particularly preferred that
Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds may be used in combination, and a solution obtained by dispersing or dispersing the organoaluminum oxy compound in the above-described inert hydrocarbon solvent. You may use.

Moreover, a borane compound and a borate compound are mentioned as another specific example of the compound (B) which reacts with a metallocene compound (A) and forms a cationic metallocene compound.
More specifically, the borane compound is represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris ( Perfluoroanthryl) borane, tris (perfluorobi) Fuchiru) such as borane and the like.

  Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula (6).
^{[L 1 -H] + [BR} 6 R 7 X 4 X 5] - (6)

In Formula (6), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium or the like.
Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In the formula (6), R ⁶ and R ⁷ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Further, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula (6) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) Borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyla Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

  Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

Moreover, the 2nd example of a borate compound is represented by following General formula (7).
[L ² ] ⁺ [BR ⁶ R ⁷ X ⁴ X ⁵ ] ⁻ (7)

In the formula (7), L ² represents carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ⁶ , R ⁷ , X ⁴ and X ⁵ are the same as defined in the general formula (6).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (o-F-Ph)} 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , NaB (3,5- (CF ₃ ) ₂ -Ph) ₄ , NaB (C ₁₀ F ₇ ) ₄ , H ⁺ BPh ₄ · 2 diethyl _{^{ethers, H + B (3,5-F}} 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 6 F}} 5) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 _{-Ph) 4} · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^ether, can be exemplified _{H + B (C 10 H 7} ) 4 · 2 diethyl ether it can.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, ^{_{H + B (C 6 F 5}} ) 4 - · 2 diethyl _{^{Ether, H + B (2,6- (CF}} 3) 2 -Ph) 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{ether, H} + B ( C ₁₀ H _{7) 4} · 2 diethyl ether.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) methylphenyl) _{borate, NaB (C 6 F 5)} 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ^{ether, H} + B ( _{2,6- (CF 3) 2 -Ph)} 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 -2 diethyl ether is mentioned.

A particularly preferred component (B) is an organoaluminum oxy compound.
By using these compounds as the component (B), and further employing specific polymerization conditions, the ethylene polymer (II) preferred in the present invention can be easily produced.

(3) Component (C)
Examples of the fine particle carrier as the component (C) include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel, and the like.

Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Table 1-14 Group elements include, for _{example, SiO 2, Al 2 O 3} , MgO, CaO, B 2 O 3, TiO 2, _{ZrO 2, Fe 2 O 3,} Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al Examples include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO.
Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited.
In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides, silica, alumina and the like is particularly preferable.

These inorganic carriers are usually calcined in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl groups is 0.8 to 1.5 mmol / g. It is preferable to adjust to use.
The properties of these inorganic carriers are not particularly limited, but usually the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1000 mm, preferably 50 to 500 mm, and the specific surface area is 150 to 1000 m. ² / g, preferably 200-700 m ² / g, pore volume 0.3-2.5 cm ³ / g, preferably 0.5-2.0 cm ³ / g, apparent specific gravity 0.10-0 It is preferred to use an inorganic carrier having a density of .50 g / cm ³ .

  Of course, the above-mentioned inorganic carriers can be used as they are, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after contacting an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

More particularly preferred components (C) include SiO ₂ , Al ₂ O ₃ , and Al ₂ O ₃ .SiO ₂ .
By using these compounds as component (C), and further by employing specific polymerization conditions, the ethylene polymer (II) preferred in the present invention can be easily produced.

(4) Contacting method, etc. The metallocene catalyst according to the present invention comprises a metallocene compound (A), a compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound, and, if necessary, a particulate carrier. The contact method of each component at the time of obtaining the catalyst which consists of (C) is not specifically limited, For example, the following methods are arbitrarily employable.

(I) After contacting the metallocene compound (A) with the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound, the fine particle carrier (C) is contacted.
(II) After contacting the metallocene compound (A) with the fine particle carrier (C), the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound is contacted.
(III) After contacting the metallocene compound (A) with the compound (B) that generates a cationic metallocene compound and the fine particle carrier (C), the metallocene compound (A) is contacted.

Of these contact methods, (I) and (III) are preferred, and (I) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.
This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, as described above, certain components are soluble when contacting the metallocene compound (A), the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound and the fine particle carrier (C). Either an aromatic hydrocarbon solvent that is hardly soluble or an aliphatic or alicyclic hydrocarbon solvent in which a certain component is insoluble or hardly soluble can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In this invention, it does not prevent performing contact reaction of each component in multiple times.

  In the present invention, the use ratio of the metallocene compound (A), the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound, and the fine particle carrier (C) is not particularly limited. A range is preferred.

When an organoaluminum oxy compound is used as the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound, the aluminum of the organoaluminum oxy compound relative to the transition metal (M) in the metallocene compound (A) is used. The atomic ratio (Al / M) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200, and when a borane compound or a borate compound is used, transition in the metallocene compound The atomic ratio (B / M) of boron to metal (M) is usually selected within the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (B) for generating a cationic metallocene compound, for each compound in the mixture, the transition metal (M) It is desirable to select at the same usage ratio as above.

  The fine particle carrier (C) is used in an amount of 0.0001-5 mmol, preferably 0.001-0.5 mmol, more preferably 0.01-0.1 mmol, of the transition metal in the metallocene compound (A). It is 1g per hit.

  The metallocene compound (A), the compound (B) that reacts with the metallocene compound (A) to form a cationic metallocene compound, and the fine particle carrier (C) are any of the contact methods (I) to (III). Then, the catalyst for olefin polymerization can be obtained as a solid catalyst by removing the solvent. The removal of the solvent is desirably performed under normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The metallocene catalyst can also be obtained by the following method.
(IV) The metallocene compound (A) and the fine particle carrier (C) are contacted to remove the solvent, which is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Make contact.
(V) The organoaluminum oxy compound, borane compound, borate compound or a mixture thereof and the fine particle carrier (C) are contacted to remove the solvent, using this as a solid catalyst component, and the metallocene compound (A) under polymerization conditions Make contact.
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

The compound (B) that reacts with the metallocene compound (A), which is an essential component of the method for producing the ethylene-based polymer (II) according to the present invention, to form a cationic metallocene compound also serves as the fine particle carrier (C). A layered silicate can also be used as a component.
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force.
Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

In general, natural products are often non-ion-exchangeable (non-swellable). In that case, in order to have preferable ion-exchange (or swellable), ion exchange (or swellable) is provided. It is preferable to perform the process for providing. Among such treatments, particularly preferred are the following chemical treatments.
Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used.
Specifically, (a) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment performed using NaOH, KOH, NH _3, etc., (c) selected from Groups 2 to 14 of the periodic table Salt treatment with a salt comprising at least one anion selected from the group consisting of a cation containing at least one atom and a halogen atom or an anion derived from an inorganic acid, (d) alcohol, hydrocarbon Examples thereof include organic compounds such as compounds, formamide and aniline. These processes may be performed independently or two or more processes may be combined.

  The layered silicate can control the particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after all the steps. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method and submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

  Of course, the above-mentioned layered silicate can be used as it is, but these layered silicates are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It can be used in combination with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

In the metallocene catalyst according to the present invention, in order to support the metallocene compound (A) on the layered silicate, the metallocene compound (A) and the layered silicate are brought into contact with each other, or the metallocene compound (A) or organoaluminum compound. The layered silicates may be brought into contact with each other.
The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
(VI) The metallocene compound (A) and the organoaluminum compound are contacted and then contacted with the layered silicate support.
(VII) The metallocene compound (A) and the layered silicate support are contacted and then contacted with the organoaluminum compound.
(VIII) The organoaluminum compound and the layered silicate support are contacted and then contacted with the metallocene compound (A).

  Of these contact methods, (VI) and (VIII) are preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. In the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed.

The use ratio of the metallocene compound (A), the organoaluminum compound, and the layered silicate carrier is not particularly limited, but the following ranges are preferable.
The supported amount of the metallocene compound (A) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support.
In the case of using an organoaluminum compound, the amount of Al supported is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.

For the method of supporting and removing the solvent, the same conditions as those for the inorganic carrier can be used.
When a layered silicate is used as a component that serves both as the catalyst component (B) and the component (C), the polymerization activity is high and the productivity of an ethylene-based polymer having a long chain branch is improved.
The olefin polymerization catalyst thus obtained may be used after the prepolymerization of the monomer if necessary.

  As an example of producing a metallocene catalyst, for example, it can be produced by referring to “catalyst” and “mixing ratio and conditions of raw materials” described in JP-T-2002-535339 and JP-A-2004-189869. it can. The index of the polymer can be controlled by various polymerization conditions, and can be controlled by, for example, the methods described in JP-A-2-269705 and JP-A-3-21607.

  The ethylene polymer (II) is an ethylene homopolymer or ethylene and an α-olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-octene and the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content therein is 0 to 40 mol%, preferably 0 to 30 mol%.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. Can do.
Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

  The ethylene polymer (II) can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method, and preferably a slurry polymerization method. Among the polymerization conditions for the ethylene polymer (II), the polymerization temperature can be selected from the range of 0 to 200 ° C. In slurry polymerization, polymerization is performed at a temperature lower than the melting point of the produced polymer. The polymerization pressure can be selected from the range of atmospheric pressure to about 10 MPa. From an aliphatic hydrocarbon such as hexane, heptane and isobutane, an aromatic hydrocarbon such as benzene, toluene and xylene, an alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, etc., in a state where oxygen, water, etc. are substantially cut off. It can be produced by carrying out slurry polymerization of ethylene and α-olefin in the presence of a selected inert hydrocarbon solvent.

  As long as the ethylene polymer (II) satisfies the specified range in the present invention, polymerization is successively performed in a single polymerizer or a plurality of reactors connected in series or in parallel, and a plurality of ethylene polymers are separated. It may be mixed after polymerization.

3. Polyethylene resin composition for containers The polyethylene resin composition for containers of the present invention is 10 to 40% by weight of ethylene polymer (II) with respect to 60 to 90% by weight of polyethylene (I) polymerized using a chromium-based catalyst. It is necessary to satisfy the following characteristics (i) to (v).
Characteristic (i): Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 1 g / 10 min.
Characteristic (ii): HLMFR is 10 to 50 g / 10 min.
Characteristic (iii): Melt flow rate ratio (HLMFR / MFR) is 60-140.
Characteristic (iv): Density is 0.940-0.970.
Characteristic (v): Melt tension (MT, 190 ° C.) is 60 mN or more.

  The blending amount of polyethylene (I) and ethylene polymer (II) is 10 to 40% by weight of ethylene polymer (II), preferably polyethylene (I), with respect to 60 to 90% by weight of polyethylene (I). 65 to 85% by weight of ethylene polymer (II) is 15 to 35% by weight, more preferably 80 to 70% by weight of polyethylene (I), and ethylene polymer (II) is 20 to 30% by weight. It is. If the blending amount is less than 10% by weight, the final resin composition cannot achieve the MFR within the specified range, and the moldability deteriorates due to the decrease in melt tension, and the environmental stress crack resistance decreases. There is a fear. On the other hand, if it exceeds 40% by weight, the MFR and density of the resin composition of the present invention will decrease, and the fluidity and rigidity may decrease, or the balance between rigidity and environmental stress crack resistance may decrease. There is.

The MFR of characteristic (i) is 0.1 to 1 g / 10 minutes, preferably 0.1 to 0.7 g / 10 minutes, and more preferably 0.2 to 0.5 g / 10 minutes.
Moreover, HLMFR of the characteristic (ii) is 10-50 g / 10min, Preferably it is 15-45g / 10min, More preferably, it is 20-40g / 10min.
When MFR and HLMFR are lower than this range, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. Moreover, when higher than this range, there exists a possibility that the deterioration of the moldability accompanying the fall of melt tension and it may become impossible to ensure environmental stress crack resistance.

  The melt flow rate ratio (HLMFR / MFR) of the characteristic (iii) is 60 to 140, and the melt flow rate ratio indicates a broad molecular weight distribution. The larger this value, the broader the molecular weight distribution. If the melt flow rate ratio is less than 60 in this range, the viscosity at a high shear rate is high due to the narrow molecular weight distribution, which may cause a problem in moldability. On the other hand, when the melt flow rate ratio exceeds 140, there is a possibility that it cannot be used for a container due to deterioration of pinch-off moldability or impact resistance due to the influence of the molecular weight distribution being too wide. The range of the melt flow rate ratio is preferably 65 to 130, more preferably 70 to 120.

  The density of characteristic (iv) is 0.940-0.970. If this density is less than 0.940, the rigidity of the container is inferior and the container tends to be deformed at a high temperature, and the container may be deformed and cause leakage due to the influence of the internal pressure of the container. On the other hand, if the density exceeds 0.970, the environmental stress crack resistance of the container may be inferior.

  The characteristic (v) melt tension (MT, 190 ° C.) is 60 mN or more. If the melt tension is less than 60 mN, a so-called draw-down phenomenon in which the parison hangs down during hollow molding tends to occur, which is not suitable for hollow molding. In particular, relatively large hollow molding is not preferable because molding may be difficult.

In this specification, MFR, MLMFR, and HLMFR are values measured according to JIS K6922-2: 1997.
MFR, MLMFR, and HLMFR can be adjusted by the ethylene polymerization temperature, the use of a chain transfer agent, or the like, and a desired product can be obtained. That is, MFR, MLMFR and HLMFR can be increased as a result of decreasing the molecular weight by increasing the polymerization temperature of ethylene and α-olefin, and MFR is increased as a result of increasing the molecular weight by decreasing the polymerization temperature. , MLMFR and HLMFR can be reduced. Also, in the copolymerization reaction of ethylene and α-olefin, the amount of hydrogen to be coexisted (chain transfer agent amount) can be increased to increase MFR, MLMFR and HLMFR as a result of lowering the molecular weight. By reducing the amount of hydrogen (chain transfer agent amount) to be generated, MFR, MLMFR and HLMFR can be reduced as a result of increasing the molecular weight.

In addition, the melt flow rate ratio of HLMFR / MFR and MLMFR / MFR can be increased or decreased by adjusting the molecular weight distribution.
The HLMFR / MFR and MLMFR / MFR are correlated with the monodispersity of the molecular weight determined by gel permeation chromatography (Q value: weight average molecular weight Mw / number average molecular weight Mn). HLMFR / MFR of 80 is monodisperse Mw / Mn is equivalent to about 16, and HLMFR / MFR of 40 corresponds to monodisperse Mw / Mn of about 6.
HLMFR / MFR, MLMFR / MFR and Mw / Mn can be adjusted by the type of catalyst, the type of promoter, the polymerization temperature, the residence time in the polymerization reactor, the number of polymerization reactors, etc. It can be adjusted by pressure, cutting speed, etc., and can be increased or decreased, preferably by adjusting the mixing ratio of high molecular weight component and low molecular weight component, and increase if the difference in average molecular weight of each component is increased Can do.

The densities of the ethylene polymer and the polyethylene resin composition are values measured according to JIS K6922-1, 2: 1997.
A desired density can be obtained by changing the density depending on the kind and amount of the comonomer copolymerized with ethylene.

The polyethylene resin composition for containers of the present invention preferably further satisfies the following characteristics (vi) to (xii).
Characteristic (vi): Peak top time (T, unit: second) and melting point (Tm, unit: ° C) in isothermal crystallization at 121.5 ° C measured by a differential scanning calorimeter (DSC) are as follows: The relationship of Formula (2) is satisfy | filled.
T ≦ −76.80 × Tm + 10410 (2)
Characteristic (vii): Both an elongation viscosity η (t) (unit: Pa · second) and an elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed.
Characteristics (viii): above, in measurement of extensional viscosity, the maximum elongation viscosity after strain hardening [eta] max (t1), when an approximate line of elongational viscosity before curing was _{η Linear (t), ηMax (} t1) / η _The strain hardening degree [λmax (0.1)] _II defined by _Linear (t1) is 1.2 to 10.0.
Characteristic (ix): tan δ at 150 ° C. and 100 rad / sec measured by a rheometer is 0.50 to 0.80.
Characteristic (x): The rupture time of the all notched creep test (FNCT, 80 ° C., 3.7 MPa) based on ISO DIS 16770 is 5 hours or more.
Characteristic (xi): The dynamic melt viscosity (η _{W · 0.01} , unit: Pa · second) at 190 ° C. _{and 0.01} rad / s measured with a rheometer is 10,000 to 100,000.
Characteristic (xii): Dynamic melt viscosity (η _{H · 0.01} , unit: Pa · second) of ethylene polymer (II) and dynamic melt viscosity (η _{W · 0.01} , unit) of polyethylene resin composition : Pa · second) (η _{H · 0.01 /} η _{W · 0.01} ) is preferably 20 or less, more preferably 10 or less.

It is preferable that the polyethylene resin composition for containers of the present invention satisfies the characteristic (vi), and the peak top time (T, unit in isothermal crystallization at 121.5 ° C. measured with a differential scanning calorimeter (DSC). : Seconds) and the melting point (Tm, unit: ° C.) preferably satisfy the relationship of the following formula (2).
T ≦ −76.80 × Tm + 10410 (2)
More preferably, it satisfies the relationship of the following formula (3), and more preferably satisfies the relationship of the following formula (4).
T ≦ −66.20 × Tm + 8771 (3)
T ≦ −54.86 × Tm + 7433 (4)
If the above formula (2) is not satisfied, the molding speed may be delayed and the molding cycle may be prolonged. Within the above range, the crystallization speed is high, the high-speed moldability is excellent, and the molding high cycle can be achieved during the container production. This value can be adjusted by the density, molecular weight and blending amount of the ethylene polymer (II). Outside the scope of the present invention, when the MFR of the ethylene polymer (II) is high, the density is low, and the blending amount is small, 121 is measured by a differential scanning calorimeter (DSC) of the polyethylene resin composition 121. The peak top time in isothermal crystallization at 5 ° C. does not satisfy the above formula (2). In addition, when the MFR of the ethylene polymer (II) is low, the density is high, and the blending amount is large outside the scope of the present invention, other requirements such as rigidity, moldability, and environmental stress crack resistance can be satisfied. Since there is a possibility that there is no, there is no reality.

Further, the polyethylene resin composition for containers of the present invention preferably satisfies the characteristic (vii), more preferably satisfies the characteristic (viii), the temperature is 170 ° C., the elongation strain rate is 0.1 (unit: 1 / second). ) Measured in both logarithmic plots of elongational viscosity η (t) (unit: Pa · second) and elongation time t (unit: second), an inflection point of elongational viscosity due to strain hardening is observed. preferable. More preferably, the degree of strain hardening [λmax (0.1)] _II is preferably 1.2 to 10. More preferably, it is 1.5-8.0, More preferably, it is 2.0-5.0.
If the inflection point of elongational viscosity due to strain hardening is not observed, strain hardening does not occur during molding, the thickness distribution of hollow molded products tends to vary, and the quality of molded products such as drop impact resistance. There is also a risk that variations will easily occur. Furthermore, if the degree of strain hardening is less than 1.2, the melt tension for fluidity is not sufficient, and the crystallization speed may be improved and the molding cycle may be delayed. [Λmax (0.1)] When _II exceeds 10, the long-chain branched structure develops too much, resulting in a decrease in the molecular weight of the fluidity balance, and there is a possibility that the environmental stress crack resistance and impact resistance may decrease. .
The observation of the inflection point of elongational viscosity resulting from strain hardening and the method of measuring the degree of strain hardening are the same as described above.

  Moreover, it is preferable that the polyethylene resin composition for containers of this invention satisfy | fills the characteristic (ix). That is, the polyethylene resin composition for containers according to the present invention has good moldability and particularly good pinch-off characteristics. It is important for the pinch-off of the hollow molded product that the shape, particularly the wall thickness, is formed relatively uniformly, and the pinch-off characteristics can be exhibited by the resin composition of the present invention. For the pinch-off characteristics, tan δ at 150 ° C. and 100 rad / sec measured with a rheometer can be cited as an index for evaluation, and tan δ is preferably 0.50 to 0.80. More preferably, it is 0.55 or more and less than 0.75. More preferably, it is 0.60 or more and less than 0.70. If this value is less than 0.50, the elastic behavior will be strong at the time of molding, and the shape of the pinch-off part will deteriorate, or the strength of the pinch-off part fusion interface will decrease, resulting in impact resistance as a container. May decrease. On the other hand, if it exceeds 0.80, the viscous behavior is too strong at the time of molding, resulting in local thinning and uneven thickness, which may reduce the impact resistance of the container. Within the above range, the hollow moldability, particularly the pinch-off part moldability is excellent, and the container has excellent environmental stress crack resistance and impact resistance. This value can be adjusted by the molecular weight and blending amount of the ethylene polymer (II), which is a high molecular weight component.

  Here, tan δ measured with a rheometer is a dynamic viscoelastic property measurement test apparatus (ARES manufactured by Reometrics), using a press sheet adjusted by hot press, 150 ° C., angular velocity 100 rad / sec. The storage elastic modulus G ′ and the loss elastic modulus G ″ are measured and calculated (tan δ = G ″ / G ′).

Furthermore, it is preferable that the polyethylene resin composition for containers of the present invention satisfies the characteristic (x), and the rupture time by an all notched creep test (FNCT, 80 ° C., 3.7 MPa) based on ISO DIS 16770, It is preferable that it is 5 hours or more. More preferably, it is over 10 hours. If it is less than 5 hours, the resistance to environmental stress cracking is inferior, and there is a risk that the container will be destroyed by the environmental stress cracking and the internal solution will leak. If it is 5 hours or more, it will be excellent in environmental stress crack resistance.
Here, the all notched creep test (FNCT) based on ISO DIS 16770 is an evaluation of long-term mechanical properties, and the sample is a razor blade on the entire circumference of a 6 mm × 6 mm × 11 mm prism. Prepare a test piece with a 1 mm notch and a cross section of 4 mm × 4 mm, and give the specimen a tensile stress equivalent to 3.7 MPa in pure water at 80 ° C. This is a value obtained by measuring the time until completion.
The breaking time of FNCT can be adjusted by the molecular weight, density and blending amount of the ethylene polymer (II), which is a high molecular weight component. Specifically, the molecular weight is increased and the density is reduced. The breaking time of the FNCT can be improved by increasing the amount and blending amount.

Further, the polyethylene resin composition for containers of the present invention preferably satisfies the characteristic (xi), and has a dynamic melt viscosity obtained when the temperature is 190 ° C. and the frequency ω is 0.01 (unit: rad / s) ( (η _{W · 0.01} , unit: Pa · second) is preferably 10,000 to 100,000. More preferably, it is 15000-80000, More preferably, it is 20000-60000. If the melt viscosity is less than 10,000, the viscosity ratio with the high molecular weight component becomes too large, so that it is difficult to disperse the high molecular weight component and the appearance of the molded product is inferior, and physical properties such as impact resistance may decrease. is there. If the melt viscosity exceeds 100,000, the fluidity is lowered and molding may be difficult.
Moreover, it is preferable that the polyethylene resin composition for containers of the present invention satisfies the characteristic (xii), and the dynamic melt viscosity η _{H · 0.01} (unit :) of the ethylene polymer (II) measured above. The ratio (η _{H · 0.01} / η _{W · 0.01} ) of the dynamic melt viscosity η _{W · 0.01} (unit: Pa · second) of the polyethylene resin composition is preferably 10 or less, More preferably, it is 8 or less. The smaller the ratio of the dynamic melt viscosities of the two, the better. If this ratio exceeds 10, the compatibility of the ethylene polymer (II) is not excellent, and the physical properties such as impact resistance, which are inferior in the appearance of the molded product, may be deteriorated.

According to the polyethylene resin composition for containers of the present invention, since it is a polyethylene material having the above characteristics (i) to (v), it is excellent in hollow moldability, environmental stress crack resistance, impact resistance, and thinner. It can be molded at a light weight, has a high crystallization speed, is excellent in high-speed moldability, can be molded in a high cycle, has good pinch-off characteristics, and has compatibility with resin components. It is possible to obtain a molded body that is high and particularly excellent in appearance of the molded body.
Furthermore, preferably, since the polyethylene material has the above characteristics (vi) to (xii) in addition to the above characteristics (i) to (v), the above effects can be further improved.

The above effect will be further described below.
That is, as described above, the ethylene polymer (II) is a specific one, and by using this together with the polyethylene (I), by using the specific ethylene polymer (II), a long chain is obtained. Due to the effect of the component having a branched structure, the crystallization rate can be increased extremely effectively, and the same effect as when a so-called crystal nucleating agent is added, the crystallization time can be shortened, and the polyethylene for containers High-speed molding and high cycle as a resin composition can be achieved.
In addition, the long chain branching structure of the ethylene-based polymer (II) makes the melt flow rate ratio specific, which enables a high degree of dispersion in polyethylene (I). The compatibility of is improved. Therefore, in the molded product, the surface properties become smooth and the appearance is particularly excellent.
Further, by using ethylene polymer (II) together with polyethylene (I), an ethylene polymer composition using a conventional chromium catalyst, an ethylene polymer composition using a Ziegler catalyst, The environmental stress crack resistance can be further improved from the ethylene polymer composition in which they are mixed.

  In conventional ethylene-based polymers, methods such as adding a substance that acts as a crystal nucleating agent have been tried to increase the crystallization speed. As a result of studying an ethylene polymer that sufficiently improves both physical properties such as mechanical strength and mechanical strength, by using the ethylene polymer (II) according to the present invention, that is, the ethylene polymer (II) is converted into polyethylene (I ), The crystallization speed can be improved sufficiently while maintaining excellent physical properties such as mechanical strength, the molding speed can be improved, and the compatibility between the two is good. And the appearance of the molded body is particularly excellent.

In the technical field to which the present invention belongs, various methods are known for measuring an ethylene-based polymer having a long-chain branched structure. For example, polymers that show rise in viscosity in elongational viscosity measurement are also known. It is contained in the ethylene-based polymer having a long chain branched structure.
Specific examples of the long-chain branched structure that regulates the molding speed include, but are not limited to, star-branched polymers and comb-branched polymers. The observed ethylene-based polymer can exhibit the effect of improving the crystallization rate.

In general, polyethylene is processed into an industrial product by a molding method that passes through a molten state such as film molding, blow molding, foam molding, etc., but at this time, elongation flow characteristics represented by the above-mentioned elongation viscosity and strain hardening degree are used. It is well known that has a great influence on the ease of molding.
That is, polyethylene having a narrow molecular weight distribution and no long chain branching has poor moldability due to its low melt strength, whereas polyethylene having an ultrahigh molecular weight component or a long chain branching component is strain-hardened (strain Hardening), that is, polyethylene having a characteristic that the extensional viscosity rapidly increases on the high strain side, and polyethylene that exhibits this characteristic remarkably is said to be excellent in moldability. Polyethylene resin having such elongation flow characteristics can prevent, for example, uneven thickness and blow-through of products in film molding and hollow molding, enables high-speed molding, and can increase the closed cell ratio during foam molding. There are benefits, such as improved strength of the molded product, improved design, lighter weight, improved molding cycle, improved heat insulation, etc., but on the other hand, if the elongational flow characteristics are too strong, The strength anisotropy presumed to be caused by the molecular orientation of the molded body causes inconveniences such as a reduction in impact strength of the molded product.
In this way, the long-chain branched structure, which is the main governing factor of the elongational viscosity property, is devised to improve the molding process surface and the disadvantages of the mechanical property of the molded body caused by the elongational flow property of polyethylene. As a result of intensive studies on the polyethylene resin composition to solve the above problem, as described above, polyethylene (I) polymerized using a chromium-based catalyst and satisfying a specific physical property balance has a high MFR main component. By using a composition of an ethylene polymer (II) having a specific long chain branched structure as a low MFR main component, that is, a high molecular weight side main component of the resin composition. In addition to excellent contribution to rigidity, environmental stress crack resistance and impact resistance improvement, it also has molding characteristics, especially hollow moldability such as drawdown resistance and pinch-off formation. Thinner and lighter, can be molded with a high melt tension, excellent draw-down resistance, can be hollow-shaped with complex shapes, and can also be improved in crystallization speed. Can be considered.

The resin composition in the present invention can contain the following substances as optional components in addition to the essential components polyethylene (I) and ethylene-based polymer (II) as long as the object of the present invention is not impaired.
For example, various ethylene polymers such as high-density polyethylene, low-density polyethylene, high-pressure polyethylene, polar monomer graft-modified polyethylene, ethylene wax, ultrahigh molecular weight polyethylene, ethylene elastomer, and modified products thereof can be used. Addition of high density polyethylene is preferable for improving rigidity, heat resistance, impact strength and the like. Addition of low density polyethylene is preferable for improving flexibility, impact strength, easy adhesion, transparency, low temperature strength and the like. Addition of high-pressure polyethylene is preferable for improving flexibility, easy adhesion, transparency, low-temperature strength, moldability, and the like. Addition of polar monomer graft-modified polyethylene such as maleic acid-modified polyethylene, ethylene / acrylic acid derivative copolymer, ethylene / vinyl acetate copolymer, flexibility, easy adhesion, colorability, compatibility with various materials, gas barrier properties, etc. It is preferable to improve. Addition of an ethylene-based wax is preferable for improving colorability, compatibility with various materials, moldability, and the like. Addition of ultrahigh molecular weight polyethylene is preferable for improving mechanical strength, wear resistance, and the like. Addition of an ethylene-based elastomer is preferable for improving flexibility, mechanical strength, impact strength, and the like.
In addition to the above polymers, various resins can be used. Specifically, various nylon resins, various polyamides, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), various polyesters, polycarbonate resin, EVOH, EVA, PMMA, PMA, various engineering plastics, polylactic acid, celluloses, Natural rubbers, polyurethanes, polyvinyl chloride, fluorine resins such as Teflon (registered trademark), inorganic polymers such as silicon resins, and the like.

The polyethylene resin composition for containers according to the present invention can be pelletized by mechanical melt mixing with a pelletizer, homogenizer or the like according to a conventional method, and then molded by various molding machines to obtain a desired molded product.
In addition, the container polyethylene resin composition obtained by the above-mentioned method includes, in addition to other olefin polymers and rubbers, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, and an antistatic agent in accordance with conventional methods. , Anti-fogging agents, anti-blocking agents, processing aids, color pigments, crosslinking agents, foaming agents, inorganic or organic fillers, flame retardants, and other known additives can be blended.
As additives, for example, one or more antioxidants (phenolic, phosphorus, sulfur), lubricants, antistatic agents, light stabilizers, ultraviolet absorbers and the like can be used in combination as appropriate. As filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. can be used. Of these, calcium carbonate, talc and mica are preferably used. In any case, the polyethylene resin composition can be blended with various additives as necessary and kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

In the present invention, it is also an effective technique to use a nucleating agent in order to further accelerate the crystallization rate of the polyethylene resin composition for containers.
As the nucleating agent, generally known nucleating agents can be used, and general organic or inorganic nucleating agents can be used. For example, dibenzylidene sorbitol or a derivative thereof, an organic phosphoric acid compound or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic carboxylic acid or a metal salt thereof, a rosin acid partial metal salt, an inorganic fine particle such as talc, an imide Amides, quinacridone quinones, or mixtures thereof.
Among them, a dibenzylidene sorbitol derivative, an organic phosphate metal salt, an organic carboxylic acid metal salt, and the like are preferable because they are excellent in transparency.
Specific examples of the dibenzylidene sorbitol derivative include 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol and 1,3: 2,4-bis (o-2,4-dimethylbenzylidene). Sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-chlorobenzylidene) sorbitol, 1,3: 2,4-dibenzylidene Sorbitol is mentioned, and specific examples of the metal salt of benzoic acid include hydroxy-di (t-butylbenzoic acid) aluminum.

  When the nucleating agent is blended in the polyethylene resin composition of the present invention, the blending amount of the nucleating agent is 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin composition comprising polyethylene (I) and ethylene polymer (II). 5 parts by weight is preferable, more preferably 0.01 to 3 parts by weight, still more preferably 0.01 to 1 part by weight, and particularly preferably 0.01 to 0.5 parts by weight. If the nucleating agent is less than 0.01 part by weight, the effect of improving the high-speed moldability is not sufficient.

4). Molded body A molded body can be produced by various molding methods using the polyethylene resin composition for containers of the present invention as a raw material. Preferably, it is mainly molded by a hollow molding method or the like, and various molded products such as a hollow container are preferably obtained.
Since the polyethylene resin composition for containers of the present invention satisfies the above characteristics, the molded article of the present invention using the polyethylene resin composition is excellent in environmental stress crack resistance and impact resistance, is thin, lightweight, smells In addition to being excellent in food safety, rigidity and heat resistance, the compatibility of the resin components is high, the surface properties of the molded article are excellent, and the appearance is particularly good. Further, it can be formed thinner and lighter, has a high crystallization speed, is excellent in high-speed moldability, can be molded in a high cycle, and has a good pinch-off characteristic.
Therefore, it is suitable for applications such as containers that require such characteristics, and in particular, containers for cosmetic containers, detergents, shampoos and rinses, or food containers such as edible oils that are required to have a good appearance. It can use suitably for a use.
In particular, a container which is a molded body using the polyethylene resin composition of the present invention can be molded at high speed and can be cycled, has excellent product characteristics, and is economically advantageous, such as detergents, shampoos and rinses. It is suitable as a container.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

1. Measurement method The measurement methods used in the examples are as follows.
(1) Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg:
Measured according to JIS K6922-2: 1997.
(2) Melt flow rate (MLMFR) at a temperature of 190 ° C. and a load of 11.1 kg:
Measured according to JIS K6922-2: 1997.
(3) Melt flow rate (HLMFR) at a temperature of 190 ° C. and a load of 21.6 kg:
Measured according to JIS K6922-2: 1997.
(4) Density:
It measured based on JIS K6922-1,2: 1997.

(5) Melt tension:
The melt tension (melt tension: MT) is determined by measuring a stress when a molten ethylene polymer is stretched at a constant speed, and can be measured under the following conditions.
[Measurement condition]
Model used: Capillograph 1B, manufactured by Toyo Seiki Seisakusho
Nozzle diameter: 2.095mm
Nozzle length: 8.0mm
Inflow angle: 180 ° (flat)
Extrusion speed: 15mm / min
Take-off speed: 6.5 m / min
Measurement temperature: 190 ° C

(6) Environmental stress crack resistance (FNCT):
A full notched creep test (FNCT) was performed according to ISO DIS 16770. A sample is prepared by preparing a test piece having a cross section of 4 mm × 4 mm in which a 1 mm notch is made with a razor blade around a 6 mm × 6 mm × 11 mm square pillar, and pure water at 80 ° C. Among them, a tensile stress corresponding to 3.7 MPa was applied to the specimen, and the time until the specimen broke was measured to obtain the FNCT breaking time.

(7) Crystallization time (crystallization rate):
The sample was allowed to stand at 190 ° C. for 5 minutes with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer Co., Ltd.), then cooled to 121.5 ° C. at a rate of 120 ° C./min, and held. The peak top was detected and measured at the time when crystallization was completed at an isothermal temperature of 121.5 ° C., and this was taken as the crystallization time.

(8) Melting point / crystallization temperature (Tm):
The melting point and the crystallization temperature are measured with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer). That is, about 5 mg of a sample obtained by cutting a 0.2 mm thick press sheet into a circle was packed in an aluminum pan, heated to 200 ° C. in a nitrogen atmosphere, held at the same temperature for 5 minutes, and 30 at 10 ° C./min. After cooling to 10 ° C. and holding at the same temperature for 5 minutes, the temperature was raised to 200 ° C. at 10 ° C./min. After that, holding at the same temperature for 5 minutes, the temperature was lowered to 30 ° C. at 10 ° C./min. The temperature at which the change in the amount of heat accompanying crystallization is maximized is defined as the melting point and the crystallization temperature (Tm).

(9) Confirmation of long chain branching structure:
Using a test piece prepared by press-molding a sheet of 18 mm x 10 mm and thickness 0.7 mm, using a rheometer (ARES manufactured by Reometrics), measurement of elongational viscosity at 170 ° C and strain rate of 0.1 / sec The presence or absence of a long chain branched structure was confirmed by the presence or absence of strain hardening (presence or absence of rising of elongational viscosity).
[Measurement condition]
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 0.1 / second-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and a thickness of 0.7 mm.
Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 0.1 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (Pa · second) on the vertical axis. On the log-log graph, the maximum elongation viscosity until strain becomes 4.0 after strain hardening is η _Max (t1) (t1 is the time when the maximum elongation viscosity is shown), and the extension viscosity before strain hardening. when the approximate line and η _linear (t), defines the value calculated as _{η Max (t1) / η linear} (t1) strain hardening degree and (.lambda.max). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time.
1 and 2 are typical plots of elongational viscosity. FIG. 1 shows a case where an inflection point of elongational viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows a case where an inflection point of elongational viscosity is not observed.

(10) Measurement of molecular weight and molecular weight distribution by gel permeation chromatography (GPC):
It measured by the gel permeation chromatography (GPC) of the following conditions.
[Measurement condition]
Model used: Alliance GPCV2000 manufactured by Nippon Waters Co., Ltd. Measurement temperature: 145 ° C
Solvent: Orthodichlorobenzene (ODCB)
Column: Showex Denko Shodex HT-806M x 2 + HT-G
Flow rate: 1.0 mL / min Injection amount: 0.3 mL

[Sample preparation]
A 3 mL sample and 3 mL of orthodichlorobenzene (containing 0.1 mg / mL 1,2,4-trimethylphenol) were weighed into a 4 mL vial, and capped with a resin screw cap and a Teflon (registered trademark) septum. Then, it melt | dissolved for 2 hours using the SSC-9300 type | mold high temperature shaker by Senshu Scientific set to the temperature of 150 degreeC. After dissolution, it was visually confirmed that there were no insoluble components.
[Create calibration curve]
Four 4 mL glass bottles are prepared, and 0.2 mg each of monodisperse polystyrene standard samples or n-alkanes of the combinations (1) to (4) below are weighed, followed by orthodichlorobenzene (0.1 mg / mL). Of SSC-9300 model manufactured by Senshu Kagaku, which was set at a temperature of 150 ° C. after weighing 3 mL (including 1,2,4-trimethylphenol) and capping with a resin screw cap and a Teflon (registered trademark) septum. Dissolution was carried out for 2 hours using a shaker.
(1) Shodex S-1460, S-66.0, n-eicosane (2) Shodex S-1950, S-152, n-tetracontane (3) Shodex S-3900, S-565, S -5.05
(4) Shodex S-7500, S-1010, S-28.5
The vial containing the sample solution was set in the apparatus, and measurement was performed under the above-described conditions. A chromatogram (retention time and differential refractometer detector response data set) was recorded at a sampling interval of 1 s. The retention time (peak apex) of each polystyrene standard sample was read from the obtained chromatogram and plotted against the logarithmic value of molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were 600 and 1200, respectively. A nonlinear least square method was applied to this plot, and the obtained quartic curve was used as a calibration curve.

[Calculation of molecular weight]
Measurement was performed under the above-mentioned conditions, and a chromatogram was recorded at a sampling interval of 1 s. This chromatogram by Sadao Mori “Size Exclusion Chromatography” (Kyoritsu Shuppan) Chapter 4 p. The differential molecular weight distribution curve and average molecular weight values (Mn, Mw and Mz) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram was corrected by the following equation. Chromatogram recording (data acquisition) and average molecular weight calculation were performed on a PC installed with Microsoft Windows XP (registered trademark) using Microsoft's own program (created with Visual Basic 6.0 from Microsoft).
H ′ = H / [1.032 + 189.2 / M (PE)]
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

(11) Melt viscosity (η _{H · 0.01} ) and zero shear viscosity (η ₀ ) of ethylene-based polymer (II):
The sample was blended with 2000 ppm of antioxidant (BASF Japan / IRGANOX B225) and melt-kneaded to form a 1.0 mm thick sheet by hot pressing, using a rheometer (ARES manufactured by Reometrics) using a parallel plate After the sample is brought into close contact with the plate and melted, the stress is relaxed at a temperature of 210 to 220 ° C., and the sample is lowered to a temperature of 190 ° C. while adjusting the plate interval so that there is no gap between the plates. Measurements were made in the range of 0 mm and strain of 0.2 to 1%. The dynamic melt viscosity (unit: Pa · second) when the frequency ω is measured at 0.01 rad / s is defined as the melt viscosity (η _{H · 0.01} ) at a low strain rate, and the frequency ω is from 100 to 0.01 rad. Using the relaxation time τ ₀ (s) and dynamic melt viscosity η ^* (unit: Pa · second) measured in the range of / s, the zero shear viscosity (η ₀ ) was calculated. The approximation of the cloth viscosity equation was calculated using a commercially available computer program by the regression method.
η ^* / η ₀ = 1 / {1+ (τ ₀ ω) ⁿ } (1)
In formula (1), n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region, and τ ₀ is a parameter representing the relaxation time.
[Measurement condition]
・ Device: Ales manufactured by Rheometrics
・ Jig: 25mm diameter parallel plate, about 1.0mm between plates
・ Measurement temperature: 190 ℃
・ Frequency range: 0.01 to 100 (unit: rad / s)
-Strain range: 0.2-1%

(12) Melt viscosity (ηW _{· 0.01} ) of the polyethylene resin composition:
Using a sample adjusted by hot pressing, a rheometer (ARES manufactured by Reometrics) was used, and a parallel plate was used at a temperature of 190 ° C. with a plate interval of 1.7 mm, a strain of 10%, and a frequency ω of 0.01 rad / s. The dynamic melt viscosity (unit: Pa · s) at that time was defined as the melt viscosity (η _{W · 0.01} ) at a low strain rate.
Measurement condition:
・ Device: Ales manufactured by Rheometrics
・ Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
・ Measurement temperature: 190 ℃
・ Frequency range: 0.01 to 100 (unit: rad / s)
・ Distortion: 10%

(12) Surface properties:
The area ratio of fish eyes was measured by the following mixing property evaluation method, and this was used as the evaluation of surface properties.
[Mixability evaluation method]
The sample to be measured is compressed at a temperature of 180 ° C. and a pressure of 100 kgf / cm ² in the first step by a mold having a thickness of 0.35 mm and two press molding machines for compression and cooling. In the second step, a press sheet having a thickness of 0.4 mm is formed by cooling at a temperature of 30 ° C. and a pressure of 50 kgf / cm ² . This press sheet was cut into a 50 × 50 × 0.4 mm test piece.
Next, the test piece was stretched with a biaxial stretching apparatus. As the biaxial stretching apparatus, a biaxial stretching apparatus SS-60 manufactured by Shibayama Scientific Instruments Co., Ltd. was used, and the test piece was stretched twice at a temperature of 150 ° C. and a stretching speed of 60 mm / min. The stretching procedure was such that the 1 cm portion of the end of the test piece was chucked by four chuck portions of the biaxial stretching device, and the unchucked central portion of the press sheet was set to a 30 × 30 mm square. Thereafter, the test piece is heated to a temperature of 130 to 170 ° C., biaxially stretched until the distance between diagonal chucks becomes 60 mm, and a sheet in which the center portion not chucked is stretched about twice is obtained. Created.
The surface of a 30 × 30 mm square region located approximately at the center of the biaxially stretched sheet was imaged using a reflective 3D microscope. The magnification of the 3D microscope is 10 times, and the range (one field of view) of the photographed sheet is 10 × 10 mm. In order to increase the reliability of the measurement, the measurement was performed four times with respect to one sample in a 30 × 30 mm square range located in the center of the sheet so that the respective fields of view do not overlap. The photographed image was binarized into a fish eye part and a non-fish eye part (uniform matrix part). The condition of the binarization process was set by a measurer, and the condition was used for all measurements.
The binarized image was read by a scanner and digitized to obtain image data.
The resolution of the scanner is 600 dpi or more, preferably 900 dpi or more. A scanner GT-F670 (manufactured by EPSON, resolution: 4800 dpi) was used as the scanner.
The analysis of the image data is realized by a personal computer and a software program executed on the personal computer, and the image data is processed by the personal computer, so that the area of each particle, the perimeter, the ratio of the major axis to the minor axis, the particle diameter, the circularity The characteristic parameters such as were calculated. In this case, the feature parameters can be calculated using commercially available image processing software or the like, and as a commercially available image analysis software, WinROOF manufactured by Mitani Corporation is used.
The image data defines a threshold value for the color arrangement of the black and white portions of the image, and is binarized and processed at an appropriate level. The condition of the binarization process was set by a measurer, and the condition was used for all measurements.
Image analysis calculates the area, perimeter, maximum length, maximum length vertical length (length in the direction perpendicular to the maximum length), etc. of each particle using known means, and the various parameters of the particles are calculated for each particle. The parameters that can be calculated are the equivalent circle diameter of the particle (diameter of the circle with the area equal to the area of the particle image), the circularity (peripheral length of the circle with the area equal to the area of the particle image) And the ratio of the perimeter of the image) and the aspect ratio (ratio of the maximum length of the particle image to the maximum vertical length of the particle).
The equivalent circle diameter is equivalent circle diameter = (area value of particle image / π) ^1/2 × 2, and the circularity is circularity = (peripheral length of circle having area value of particle image) / ( The peripheral length of the particle image) and the aspect ratio are calculated by (maximum length of the particle image) / (maximum vertical length of the particle image).
In the present invention, as the measurement of fish eyes, the area ratio of fish eyes in the image was determined. For the area ratio of one sample of fish eye, the average value of the measured values obtained for each of the four visual fields photographed on one test piece was calculated.
And, when the area ratio of the fish eye in the image is 0.2% or less, “1”, when it is more than 0.2 to 0.5%, “2”, more than 0.5 to 3.0% The case was evaluated as “3”, the case of over 3.0 to 5.0% as “4”, and the case of over 5% as “5”. The evaluation results are shown in Table 2.

(11) Overall evaluation:
The suitability of the hollow moldability as a polyethylene resin composition for containers was evaluated, and “Good” was given for any of the following items, and “X” was given for the other items.
That is, the following pinch-off characteristics, resistance to drawdown, crystallization time and elongational viscosity were measured.
1) Pinch-off characteristics: tan δ measurement at 150 ° C. and 100 rad / sec measured with a rheometer is performed using a sample adjusted by a hot press, using a rheometer (ARES manufactured by Reometrics) at 150 ° C. and an angular velocity of 100 rad / sec. The storage elastic modulus G ′ and the loss elastic modulus G ″ were measured, and tan δ (= G ″ / G ′) was calculated. The measurement conditions are described below. When tan δ is 0.50 to 0.80, the pinch-off characteristics are good.
[Measurement condition]
・ Device: Ales manufactured by Rheometrics
・ Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
・ Measurement temperature: 150 ℃
・ Distortion: 10%
2) Draw-down resistance: Good with a melt tension (melt tension: MT) of 60 mN or more.
3) Crystallization rate: DSC isothermal crystallization time satisfying the formula (2) was considered good.
T [sec] ≦ −76.80 × Tm [° C.] + 10410 (2)
(T [sec]: peak top time in isothermal crystallization at 121.5 ° C. measured with a differential scanning calorimeter (DSC), Tm [° C.]: melting point)
4) A product having a rising elongation viscosity confirmed to be good.

2. Examples and Comparative Examples <Synthesis of Metallocene Complex (1)>
According to the method disclosed in Example 3 of JP2009-96907A, dimethylsilylenebis (2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) is used as the metallocene complex (1). ) -Indenyl) zirconium dichloride was synthesized.

<Preparation of solid catalyst A>
To 17 ml of toluene were added 8.5 ml (25 mmol) of a toluene solution of methylalumoxane (Albemarle, Al concentration: 2.93 mol / L) and 105 mg of metallocene complex (1), and the mixture was stirred at room temperature for 30 minutes under light shielding to form a catalyst. A component solution was obtained.
Next, the above catalyst component solution was added to 5.0 g of SiO ₂ (manufactured by GRACE, Sylpol 2212, average particle size 12 μ) calcined at 600 ° C. for 8 hours under a nitrogen atmosphere, and stirred at 40 ° C. for 1 hour. Thereafter, vacuum drying was performed while maintaining 40 ° C. to obtain a solid catalyst A.
[Example 1]
<Ethylene polymer I>
A polyethylene grade polymerized by a commercially available chromium catalyst (Novatec HD: HB439RP, manufactured by Nippon Polyethylene Co., Ltd.) was used as the ethylene polymer I (E1). The physical property values of the polymer (E1) are shown in Table 1.

<Production of polymer with metallocene catalyst>
<Production of ethylene copolymer (II)>
To an autoclave with an internal volume of 1.5 L purged with nitrogen, 1 mmol of triisobutylaluminum, 2 ml of a 2% hexane solution of STADIS 450 and 1 ml of 1-hexene were added, and 800 ml of isobutane was introduced. The internal temperature of the autoclave was raised to 80 ° C., 70 ml of hydrogen was added, and ethylene was introduced so that the ethylene partial pressure was 1.0 MPa. Next, 27 mg of the solid catalyst A was introduced into the autoclave to initiate polymerization. During the polymerization, ethylene was added so as to maintain 80 ° C. and an ethylene partial pressure of 1.0 MPa. Further, in order to keep the hydrogen concentration during the polymerization constant, the hydrogen concentration in the gas phase part of the autoclave was measured, and the polymerization was continued while appropriately adding hydrogen. Further, 1-hexene was continuously supplied at a ratio of 2 wt% of the added ethylene. After 2 hours, the reaction was stopped by purging the internal pressure of the autoclave and isobutane.
As a result, 265 g of polymer was recovered. The average hydrogen / ethylene molar ratio of the gas phase portion during polymerization was 0.17%. As a result of evaluating the physical properties of the obtained polymer, HLMFR was 0.42 g / 10 min, density was 0.9255 kg / m ³ , Mw was 310,000, Mw / Mn was 3.4, and HLMFR / MFR was 23. The physical property values of (E4) are shown in Table 1. The polymer (E4) exhibited a relatively large HLMFR / MFR in proportion to the molecular weight distribution, and thus had a long-chain branched structure.

<Manufacture of polyethylene resin composition>
The polyethylene (I) (E1) and the ethylene polymer (II) (E4) were melt-mixed at the ratio shown in Table 1 under the following kneading conditions to produce a polyethylene resin composition.
[Kneading conditions]
Used equipment:
Lab-plast mill roller mixer (mixer model: R100 / blade shape: roller type R100B) manufactured by Toyo Seiki Seisakusho Co., Ltd.
Additive formulation:
BASF Japan / IRGANOX B225: 2000ppm
Tamnan Chemical Industry / Calcium stearate: 1000ppm
Filling amount: 70 g / batch
Kneading temperature: 190 ° C
Blade rotation speed: 40rpm
Preheating time: 5 minutes Kneading time: 2 minutes

  The physical properties and evaluation results of the resin composition are shown in Table 2. The resulting composition has good compatibility of each component, a short crystallization time, excellent molding high cycleability, excellent fluidity and high melt tension, and excellent hollow moldability. Excellent mechanical properties such as environmental stress cracking balance and impact resistance.

[Examples 2 to 5]
The same procedure as in Example 1 was performed except that conditions were set for the amount of 1-hexene as a comonomer and the amount of hydrogen as a chain transfer agent so that the composition shown in Table 1 was obtained. The evaluation results of the obtained polymer and polymer composition are shown in Table 1. That is, (E1) was used as polyethylene (I), and (E4) to (E6) were used as ethylene-based polymer (II). Polymers (E4) to (E6) exhibited a relatively large HLMFR / MFR in terms of molecular weight distribution, and thus had a long-chain branched structure. The obtained polymer composition has good compatibility of each component, high melt tension, short crystallization time, excellent molding high cycle property, and machine such as environmental stress crack resistance and impact resistance. Excellent physical properties.

[Comparative Example 1]
<Manufacture of Ziegler catalyst>
As the solid catalyst component, a Ti-based catalyst obtained by a dissolution precipitation method was used. The manufacturing method is as follows.
The inside of a 1 liter three-necked flask equipped with a stirrer and a condenser was sufficiently purged with nitrogen, and then dried hexane 250 ml, anhydrous magnesium chloride 11.4 g previously pulverized in a 3 liter vibration mill for 1 hour and n -110 ml of butanol was added and heated at 68 ° C for 2 hours to obtain a uniform solution (1a).
After cooling this solution (1a) to room temperature, 8 g of methylpolysiloxane having a kinematic viscosity at 25 ° C. of 25 cSt was added and stirred for 1 hour to obtain a uniform solution (1b).
Next, after the solution (1b) was cooled with water, 50 ml of titanium tetrachloride and 50 ml of dry hexane were dropped into the solution using a dropping funnel over 1 hour to obtain a solution (1c). The solution (1c) was uniform, and the complex of the reaction product was not precipitated.
The solution (1c) was heated at 68 ° C. for 2 hours while refluxing. About 30 minutes after the start of heating, precipitation of the reaction product complex (1d) was observed. This was collected, washed 6 times with 250 ml of dry hexane, and further dried with nitrogen gas to recover 19 g of the reaction product complex (1d).
When the reaction product complex (1d) was analyzed, it contained Mg 14.5% by mass, n-butanol 44.9% by mass and Ti 0.3% by mass, and the specific surface area was 17 m ² / g. .

Next, 4.5 g of the reaction product complex (1d) was collected in a 1-liter three-necked flask equipped with a stirrer and a condenser under a nitrogen atmosphere, and 250 ml of dry hexane and 25 ml of titanium tetrachloride were added thereto. The mixture was heat-treated at 68 ° C. for 2 hours under reflux, cooled to room temperature, washed 6 times with 250 ml of dry hexane, and dried with nitrogen gas to recover 4.6 g of the solid catalyst component (1e).
When this solid catalyst component (1e) was analyzed, it contained 12.5% by mass of Mg, 17.0% by mass of n-butanol and 9.0% by mass of Ti, and the specific surface area was 29 m ² / g. . When this solid catalyst component (1e) was observed with an SEM, the particle size was uniform and the shape was close to a sphere.

<Manufacture of polymer>
The solid catalyst component (1e) 0.79 g / hr obtained in the production of the catalyst from the catalyst supply line and the triisobutylaluminum (TIBAL) were organically added to the liquid-filled loop type first stage reactor having an internal volume of 145 liters. While supplying continuously from the metal compound supply line at a rate of 0.2 mmol / hr and discharging the polymerization contents at the required rate, dehydration-purified isobutane 160 (l / hr), hydrogen 14 (G / hr), ethylene was fed at a rate of 11.5 (kg / hr), and the first stage polymerization was continuously carried out under the conditions of a total pressure of 4.2 MPa and an average residence time of 0.8 hours.
A part of the polymerization product in the first-stage reactor was collected, and the polymer was collected and measured for physical properties. As a result, MFR = 20.0 g / 10 min and D = 0.9648 kg / m ³ .

The entire amount of the slurry-like polymerization product produced in the first stage reactor is directly introduced into the second stage reactor having an internal volume of 290 liters, and the contents of the polymerizer are discharged at the required speed without adding a catalyst. At 95 ° C., dehydrated and purified isobutane 160 (l / hr), hydrogen 10 (g / hr), and ethylene 10.0 (kg / hr) were supplied at a total pressure of 4.2 MPa and an average residence time of 0 The second stage polymerization was carried out continuously under the condition of .8Hr.
The polymerization product discharged from the second stage reactor was introduced into a flushing tank, the polymerization product was continuously withdrawn, and unreacted gas was removed from the degassing line.
As a result of evaluating physical properties of the obtained polymer, MFR = 17.0, D = 0.640 kg / m ³ , polyethylene (I) of this polymer was defined as (E2), and the results are shown in Table 1.

<Manufacture of polyethylene resin composition>
The polyethylene (I) (E2) and the ethylene-based polymer (II) (E4) were melt-mixed in the proportions shown in Table 1 in the same manner as in Example 1 to produce a polyethylene resin composition.
From Tables 1 and 2, since Comparative Example 1 does not satisfy the specific matters of the present invention because the ethylene polymer (I) is not polyethylene polymerized by a chromium catalyst, the balance between density and environmental stress crack resistance, Although the mechanical properties such as impact properties were extremely excellent, the compatibility of each component was not sufficient, the appearance of the molded product was poor, the crystallization time for density matching was long, and the molding high cycle property was poor.

[Comparative Examples 2 to 4]
The polymerization of ethylene in Comparative Example 1 was performed in the same manner as in Example 1 except that conditions were set for the amount of 1-hexene as a comonomer and the amount of hydrogen as a chain transfer agent so that the composition shown in Table 1 was obtained. The evaluation results of the obtained polymer and polymer composition are shown in Table 1. That is, (E2) and (E3) were used as polyethylene (I), and (E4) to (E6) were used as ethylene polymer (II). The evaluation results of the obtained polymers and polymer compositions are shown in Tables 1 and 2.
From Tables 1 and 2, Comparative Examples 2 to 3 do not satisfy the specific matters of the present invention because the ethylene polymer (I) is not polyethylene polymerized by a chromium catalyst, and balance between density and environmental stress crack resistance. Although the mechanical properties such as impact resistance are extremely excellent, the compatibility of each component is insufficient, the appearance of the molded product is poor, the crystallization time for density is long, and the molding high cycle property is poor. It was. Further, regarding Comparative Example 4, the compatibility of each component was good, but the melt tension was low, the crystallization time for the density was long, and the molding high cycle property was bad.

[Comparative Example 5]
The same procedure as in Example 1 was performed except that conditions were set for the amount of 1-hexene as a comonomer and the amount of hydrogen as a chain transfer agent so that the composition shown in Table 1 was obtained. That is, (E1) was used as polyethylene (I), and (E6) was used as ethylene polymer (II). The polymer (E6) exhibited a relatively large HLMFR / MFR in proportion to the molecular weight distribution, and thus had a long-chain branched structure. The evaluation results of the obtained polymers and polymer compositions are shown in Tables 1 and 2.
From Tables 1 and 2, Comparative Example 5 reached a good balance as a polyethylene resin composition for containers by using polyethylene polymerized with a chromium catalyst as the ethylene polymer (I). Since the blending amount of each polyethylene component does not satisfy the specific matter of the present invention, sufficient fluidity cannot be maintained as a polyethylene resin composition for containers, resulting in inferior resin extrusion characteristics with a molding machine screw.

[Comparative Example 6]
The same procedure as in Example 1 was performed except that conditions were set for the amount of 1-hexene as a comonomer and the amount of hydrogen as a chain transfer agent so that the composition shown in Table 1 was obtained. That is, (E3) was used as polyethylene (I), and (E7) was used as ethylene polymer (II). The polymer (E7) exhibited a relatively large HLMFR / MFR in proportion to the molecular weight distribution, and thus had a long-chain branched structure. The evaluation results of the obtained polymers and polymer compositions are shown in Tables 1 and 2.
From Tables 1 and 2, since Comparative Example 6 shows that the HLMFR, η _{H · 0.01} and η ₀ of the ethylene polymer (II) do not satisfy the specific matters of the present invention, the viscosity ratio of each polymer component is It became too large, and as a polyethylene resin composition for containers, the compatibility of the resin component was extremely poor.

[Reference Example 1]
A polyethylene grade polymerized by a commercially available chromium-based catalyst (Nippon Polyethylene Co., Ltd., Novatec HD: HB423RN) was evaluated as a polyethylene resin composition for containers, and the evaluation results are shown in Table 2.
From Table 2, the polyethylene polymerized with the chromium catalyst was inferior to the density-matched FNCT as compared with the polyethylene polymerized with the metallocene catalyst.

[Reference Example 2]
A polyethylene grade polymerized by a commercially available chromium catalyst (Nippon Polyethylene, Novatec HD: HB332R) was evaluated as a polyethylene resin composition for containers, and the evaluation results are shown in Table 2.
From Table 2, the polyethylene polymerized with the chromium catalyst was inferior to the density-matched FNCT as compared with the polyethylene polymerized with the metallocene catalyst.

According to the present invention, it is excellent in hollow moldability, environmental stress crack resistance and impact resistance, can be molded thinner and lighter, has a high crystallization speed, excellent high-speed moldability, and has a high molding cycle. It is possible to provide a polyethylene resin composition for containers and a molded body comprising the same, which have good pinch-off characteristics, high compatibility of resin components, and particularly excellent appearance of the molded body.
Furthermore, it is excellent in high fluidity, odor, food safety, rigidity, heat resistance and the like.
Therefore, it is suitable for applications such as containers that require such characteristics, and particularly suitable for applications such as cosmetic containers having excellent appearance, containers for detergents, shampoos and rinses, or food containers such as edible oils. it can.
Furthermore, the container using the polyethylene resin composition of the present invention can be molded at high speed and high cycle, has excellent product characteristics, and is economically advantageous, such as cosmetic containers, detergents, shampoos and rinses. Suitable as a container.
Further, since the polyethylene resin composition of the present invention is excellent in performance as described above, it can be suitably used for kerosene cans, chemical containers, and the like that require such characteristics in addition to the above containers. This is very useful in industry.

Claims (11)

60-90% by weight of polyethylene (I) polymerized using a chromium-based catalyst is polymerized using a metallocene-based catalyst containing Ti, Zr or Hf, and a melt flow rate at a temperature of 190 ° C. and a load of 21.6 kg. (HLMFR) is 0.2 g / 10 min or more and less than 5 g / 10 min, density (D) is 0.915 to 0.945 g / cm ³ , and an ethylene-based polymer (II) having a long-chain branched structure A polyethylene resin composition for containers comprising 10 to 40% by weight and satisfying the following characteristics (i) to (v).
Characteristic (i): Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 1 g / 10 min.
Characteristic (ii): HLMFR is 10 to 50 g / 10 min.
Characteristic (iii): Melt flow rate ratio (HLMFR / MFR) is 60-140.
Characteristic (iv): Density is 0.940-0.970 g / cm ³ .
Characteristic (v): Melt tension (MT, 190 ° C.) is 60 mN or more. The polyethylene resin composition for containers according to claim 1, wherein the ethylene polymer (II) satisfies the following property (a):
Characteristic (A): Melt flow rate ratio (HLMFR / MFR) is 10-35. The polyethylene resin composition for containers according to claim 1 or 2, wherein the ethylene polymer (II) satisfies the following characteristics (b).
Characteristic (b): Dynamic melt viscosity (η _{H · 0.01} , unit: Pa · second) measured when the frequency ω is 0.01 rad / s at a temperature of 190 ° C. is 100,000 to 1,000,000. It is. The polyethylene resin composition for containers according to any one of claims 1 to 3, wherein the ethylene polymer (II) satisfies the following characteristics (c).
Characteristics (c): Zero when a dynamic melt viscosity η ^* (unit: Pa · second) measured at a temperature ω of 190 ° C. in the range of 100 to 0.01 rad / s is approximated by the following formula (1) The shear viscosity (η ₀ , unit: Pa · second) is 100,000 to 1,000,000.
η ^* / η ₀ = 1 / {1+ (τ ₀ ω) ⁿ ) (1)
(In the formula (1), τ ₀ is a parameter representing the relaxation time, and n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region.) The polyethylene resin composition for containers according to any one of claims 1 to 4, wherein the polyethylene (I) satisfies the following characteristics (A) to (D).
Characteristic (A): MFR is 0.1 to 10 g / 10 min.
Characteristic (B): Melt flow rate (MLMFR) at a temperature of 190 ° C. and a load of 11.1 kg is 1 to 50 g / 10 min.
Characteristic (C): Melt flow rate ratio (MLMFR / MFR) is 10-30.
Characteristic (D): Density is 0.950 to 0.965 g / cm ³ . Furthermore, the following characteristic (vi) is satisfied, The polyethylene resin composition for containers of any one of Claims 1-5 characterized by the above-mentioned.
Characteristic (vi): Peak top time (T) and melting point (Tm) in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) satisfy the relationship of the following formula (2).
T [sec] ≦ −76.80 × Tm [° C.] + 10410 (2) Furthermore, the following characteristic (vii) is satisfied, The polyethylene resin composition for containers of any one of Claims 1-6 characterized by the above-mentioned.
Characteristic (vii): Both an elongation viscosity η (t) (unit: Pa · second) and an elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed.   The container according to any one of claims 1 to 7, wherein the ethylene polymer (II) is polymerized using a metallocene catalyst having a cyclopentadienyl ring and a heterocyclic aromatic group. Polyethylene resin composition.   The polyethylene resin composition for containers according to claim 8, wherein the metallocene catalyst has an indenyl ring skeleton.   A molded article comprising the polyethylene resin composition for containers according to any one of claims 1 to 9.   The molded body according to claim 10, which is produced by a hollow molding method.